WO2012073476A1 - セラミックヒータ素子、セラミックヒータ、およびグロープラグ - Google Patents
セラミックヒータ素子、セラミックヒータ、およびグロープラグ Download PDFInfo
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- WO2012073476A1 WO2012073476A1 PCT/JP2011/006624 JP2011006624W WO2012073476A1 WO 2012073476 A1 WO2012073476 A1 WO 2012073476A1 JP 2011006624 W JP2011006624 W JP 2011006624W WO 2012073476 A1 WO2012073476 A1 WO 2012073476A1
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- WIPO (PCT)
- Prior art keywords
- sialon
- ceramic heater
- heater element
- heating resistor
- ratio
- Prior art date
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- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 150000004767 nitrides Chemical class 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
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- 150000001247 metal acetylides Chemical class 0.000 claims description 12
- 229910003564 SiAlON Inorganic materials 0.000 abstract 8
- 239000000126 substance Substances 0.000 abstract 1
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- 238000010304 firing Methods 0.000 description 32
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 229910052692 Dysprosium Inorganic materials 0.000 description 9
- 230000003247 decreasing effect Effects 0.000 description 9
- 229910052706 scandium Inorganic materials 0.000 description 9
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- 238000013459 approach Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
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- 229910019974 CrSi Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23Q—IGNITION; EXTINGUISHING-DEVICES
- F23Q7/00—Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
- F23Q7/001—Glowing plugs for internal-combustion engines
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
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- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/027—Heaters specially adapted for glow plug igniters
Definitions
- the present invention relates to a ceramic heater element, a ceramic heater, and a glow plug.
- heater elements are used for glow plugs for promoting start-up of diesel engines, ignition heaters for burners, heaters for gas sensors, and the like.
- the heater element include a metal sheath heater element in which a heat-resistant insulating powder is filled in a metal sheath and a coil-shaped heating element is embedded in the heat-resistant insulating powder, or a conductive ceramic in a base made of an insulating ceramic.
- a ceramic heater element in which a heating resistor is embedded is known, and is appropriately selected and used.
- the grain boundary phase for improving the sinterability, the thermal expansion coefficient is brought close to the thermal expansion coefficient of the heating resistor, and cracks are caused by thermal stress.
- production of this is known.
- the grain boundary phase for example, those containing rare earth elements are known, and as the thermal expansion coefficient adjusting material, for example, chromium silicide is known.
- the heating resistor in the ceramic heater element for example, at least one selected from silicides, nitrides, and carbides of Mo and silicides, nitrides, and carbides of W is used as a main phase, and silicon nitride And what has a grain boundary phase for improving sinterability is known.
- the grain boundary phase for example, those containing rare earth elements are known as in the case of the grain boundary phase of the substrate (for example, see Patent Document 1).
- Such a ceramic heater element is required to consume less power and to be excellent in rapid temperature rise.
- a method of suppressing power consumption and improving rapid temperature rising property a method of combining resistors having different resistances (for example, see Patent Document 2), a method of reducing a heat generating material cross-sectional area at a position where heat is generated (for example, Patent Document) 3)), etc. are being studied from the structural aspect.
- the method of combining resistors having different resistances increases the number of man-hours required for manufacturing and tends to increase the manufacturing cost.
- the method of reducing the heat generating material cross-sectional area requires that the temperature of the resistor be excessively high, and there is a risk that the energization durability may be reduced.
- improvement from the structural aspect has problems such as productivity and durability, it is required to suppress power consumption and improve rapid temperature rise by other methods.
- ceramic heater elements are required to have good sinterability, heat resistance, oxidation resistance at high temperatures, etc. in addition to the power consumption and rapid temperature rise described above.
- a hot press firing method is used. Need to apply. When the hot press firing method is applied, the number of man-hours required for production increases and the production cost tends to increase.
- the present invention has been made in order to solve the above-described problems, and an object thereof is to provide a ceramic heater element that has low power consumption, excellent rapid temperature rise characteristics, and excellent productivity, high temperature characteristics, and the like. It is said. Another object of the present invention is to provide a ceramic heater and a glow plug using such a ceramic heater element.
- the ceramic heater element of the present invention has an insulating base and a heating resistor embedded in the insulating base.
- the insulating substrate has ⁇ -sialon or ⁇ -sialon and ⁇ -sialon mixed phase sialon as a main phase, a grain boundary phase containing a rare earth element, and at least selected from Cr, W, Mo, V, and Fe It is characterized by having one kind of silicide.
- the heating resistor is composed of a conductive compound composed of at least one selected from Mo silicides, nitrides and carbides, and W silicides, nitrides and carbides as a main phase, and ⁇ -sialon. Alternatively, it is characterized by having a mixed phase sialon of ⁇ -sialon and ⁇ -sialon and a grain boundary phase containing a rare earth element.
- the ceramic heater of the present invention is a ceramic heater having a ceramic heater element and a metal outer cylinder that holds the ceramic heater element inside so that a tip portion protrudes, the ceramic heater element of the present invention described above. It is a ceramic heater element.
- the glow plug of the present invention is a glow plug including a ceramic heater and a cylindrical metal shell that holds the rear end portion of the ceramic heater therein, and the ceramic heater is the ceramic heater of the present invention described above. It is characterized by that.
- the ceramic heater element of the present invention by setting the composition of the insulating base and the heating resistor to a specific composition, the power consumption is low, the rapid temperature rising property is excellent, and the productivity, high temperature characteristics, etc. are also good. can do.
- having the ceramic heater element of the present invention has low power consumption, excellent rapid temperature rise characteristics, and good productivity, high temperature characteristics, and the like. be able to.
- Sectional drawing which shows an example of the glow plug which has a ceramic heater element of this invention.
- FIG. 1 shows an example of a glow plug having a ceramic heater element of the present invention (hereinafter simply referred to as a heater element).
- FIG. 1A is a longitudinal sectional view of the entire glow plug
- FIG. 1B is a sectional view of the ceramic heater element portion.
- the glow plug 1 has a ceramic heater 2 and a cylindrical metal shell 3 that holds the rear end of the ceramic heater 2 inside.
- a screw portion 31 is formed as an attachment portion for fixing the glow plug 1 to an engine block (not shown).
- a metal shaft 4 for supplying electric power to the ceramic heater 2 from the rear end side is disposed in the metal shell 3 in an insulated state from the metal shell 3.
- an insulating bush 5 made of an insulating material is disposed between the rear end side outer peripheral surface of the metal shaft 4 and the inner peripheral surface of the metal shell 3.
- an insulating material such as rubber is used in contact with the inner hole of the metal shell 3, the metal shaft 4 and the insulating bush 5 in order to improve the airtightness inside the metal shell 3.
- An O-ring 6 is arranged.
- the rear end portion of the metal shaft 4 extends to the rear of the metal shell 3, and a terminal metal fitting 8 is fitted into the extended portion via an insulating bush 5.
- the terminal fitting 8 is fixed to the outer peripheral surface of the metal shaft 4 in a conductive state by a caulking portion 8a in the circumferential direction.
- the ceramic heater 2 has the heater element 10 of the present invention and a metal outer cylinder 11 that holds the heater element 10 inside so that the tip portion protrudes.
- the metal shell 3 and the metal outer cylinder 11 are, for example, a small-diameter portion 11 s at the rear end of the metal outer cylinder 11 is press-fitted into the tip of the inner hole of the metal shell 3 and the large-diameter portion 11 b at the center and the tip of the metal shell 3 The part is fixed by laser welding all around.
- the heater element 10 of the present invention has a rod-like form in which a heating resistor 102 is embedded in an insulating substrate 101.
- the heating resistor 102 has a U-shaped heating portion 103 disposed on the front end side of the heater element 10 and a pair of linear shapes connected to both ends and extending along the direction of the axis CL1 of the heater element 10.
- Lead part 104 One lead portion 104 is electrically connected to the metal shell 3 via the metal outer cylinder 11 by a grounding energizing terminal portion 12 protruding in the radial direction.
- the other lead portion 104 has a power supply side energizing terminal portion 13 projecting in the same manner and is electrically connected to a metal ring 14 fitted to the rear end portion of the heater element 10. This ring 14 is fixed to and electrically connected to the tip end of the metal shaft 4 by welding or the like, and thereby, power is supplied to the heater element 10.
- the insulating substrate 101 has ⁇ -sialon or a mixed phase sialon of ⁇ -sialon and ⁇ -sialon as a main phase, and further includes a grain boundary phase containing a rare earth element, Cr, W, Mo, It is characterized by having at least one silicide selected from V and Fe.
- the heating resistor 102 is mainly composed of a conductive compound of at least one selected from Mo silicides, nitrides and carbides, and W silicides, nitrides and carbides, and ⁇ - It is characterized by having sialon or ⁇ -sialon and ⁇ -sialon mixed phase sialon and a grain boundary phase containing rare earth elements.
- the main phase of the insulating base 101 and the insulating component of the heating resistor 102 are made of sialon, it is possible to suppress power consumption and improve rapid temperature rise. That is, since sialon has a smaller thermal conductivity than silicon nitride, it is possible to suppress the heat generated by the heater element 10 from escaping to another member for fixing the heater element 10. As a result, heating can be performed efficiently, power consumption can be suppressed, and rapid temperature rise can be improved.
- silicon nitride has a high thermal conductivity, so that it cannot be heated efficiently, consumes a large amount of power, and deteriorates rapid temperature rise. End up.
- silicon nitride has a high thermal conductivity, so that it cannot be heated efficiently, consumes a large amount of power, and deteriorates rapid temperature rise. End up.
- a sintering aid for improving the sinterability, particularly the denseness, It is easy to deteriorate.
- the amount of the sintering aid is reduced with emphasis on oxidation resistance, the sinterability decreases and the strength decreases.
- the thermal conductivity at room temperature is 30 to 100 W / mK for silicon nitride and 10 to 20 W / mK for sialon.
- sialon As the main phase of the insulating substrate 101, productivity can be improved while achieving both oxidation resistance and sinterability. Further, by using both the main phase of the insulating substrate 101 and the insulating component of the heating resistor 102 as sialon, the sintering behavior and heat shrinkage of both the insulating substrate 101 and the heating resistor 102 can be matched. Therefore, at the time of manufacturing, particularly at the time of sintering, it is possible to suppress the occurrence and the like of cutting and breakage of the heating resistor 102 and peeling at the interface between the insulating substrate 101 and the heating resistor 102. In use, durability against repeated temperature increases can be improved. In particular, since the insulating base 101 has at least one silicide selected from Cr, W, Mo, V, and Fe, the thermal expansion coefficient of the insulating base 101 becomes the thermal expansion coefficient of the heating resistor 102. The durability against repeated heating increases.
- the insulating base 101 and the heating resistor 102 will be specifically described.
- the insulating substrate 101 has ⁇ -sialon or a mixed phase sialon of ⁇ -sialon and ⁇ -sialon as a main phase.
- the main phase means the phase with the largest mass among the constituent phases.
- the heating resistor 102 is also configured with the same sialon.
- Sialon is a solution in which an auxiliary component is dissolved in a lattice of Si 3 N 4 , and ⁇ -sialon represented by a composition formula Si 6-z Al z O z N 8-z (0 ⁇ Z ⁇ 4.2). And the composition formula Mx (Si, Al) 12 (O, N) 16 (0 ⁇ X ⁇ 2, M is Li, Mg, Ca, Y, R (R is a rare earth element excluding La and Ce)). ⁇ -sialon exists.
- ⁇ -sialon is a structure in which needle-like particles are intertwined in a complex manner like silicon nitride, high strength and toughness can be obtained.
- ⁇ -sialon has an equiaxed particle shape and thus has low toughness, but can have higher hardness than ⁇ -sialon.
- Yb and the like Li, Mg, Ca, Y, R (R is a rare earth element other than La and Ce)
- the grain boundary phase is reduced and oxidation resistance is improved.However, when only ⁇ -sialon is used, the grain boundary phase component is added to sialon during sintering. Therefore, it is impossible to obtain a dense sintered body because it is taken in and is almost lost, so that ⁇ -sialon particles and ⁇ -sialon particles are simultaneously generated to provide excellent sinterability and oxidation resistance. A product excellent in properties and strength can be obtained.
- the ratio of ⁇ -sialon ( ⁇ ratio) in the sialon ( ⁇ -sialon and ⁇ -sialon) of the insulating substrate 101 is not necessarily limited, but if the ⁇ ratio is low, the ratio of the grain boundary phase increases. 2% or more is preferable because oxidation resistance tends to decrease. On the other hand, when the ⁇ ratio is high, the grain boundary phase component is taken into the sialon during the sintering and almost disappears, so that a dense sintered body cannot be obtained. As a result, the strength and durability against repeated temperature increases are likely to decrease, so 60% or less is preferable. From the viewpoint of making the strength and durability against repeated heating higher, the ⁇ ratio is preferably 50% or less, and more preferably 30% or less.
- the ⁇ rate in the insulating substrate 101 is preferably higher than the ⁇ rate in the heating resistor 102. Specifically, it is in the range of 2 to 50%, more preferably in the range of 2 to 30% as described above. It is preferable that the ⁇ rate in the heating resistor 102 is higher.
- the ⁇ rate is ⁇ 1 for the (101) plane peak intensity of ⁇ -sialon, ⁇ 2 for the (210) plane peak intensity of the ⁇ -sialon, and ⁇ 1 for the (102) plane peak intensity of the ⁇ -sialon in the X-ray diffraction pattern.
- the peak intensity is ⁇ 2
- ( ⁇ 1 + ⁇ 2) / ( ⁇ 1 + ⁇ 2 + ⁇ 1 + ⁇ 2) is calculated.
- the Z value representing the solid solution amount of alumina in ⁇ -sialon in the insulating substrate 101 is not necessarily limited, but is preferably 0.1 or more, more preferably 0.3 or more from the viewpoint of obtaining sufficient sinterability. .
- the value is preferably 1.3 or less, more preferably 1.0 or less, and particularly preferably 0.8 or less.
- the Z value is calculated from the difference between the a-axis lattice constant of ⁇ -sialon in the sialon phase measured by X-ray diffraction measurement and the a-axis lattice constant of ⁇ -silicon nitride (7.604442 ⁇ ⁇ ). There is a calculation method (for example, refer to WO 02/44104, page 28).
- the grain boundary phase in the insulating substrate 101 is solidified during cooling after the sintering aid added to promote the sintering becomes a liquid phase and contributes to the generation, rearrangement, and grain growth of sialon (particles). It was produced as a glass or crystalline phase.
- This grain boundary phase contains rare earth elements, specifically, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and It contains at least one selected from Lu. Among these, at least selected from Sc, Y, Dy, Er, Yb, and Lu since crystallization of the grain boundary phase can be promoted, the high temperature strength can be improved, and the ⁇ ratio can be easily adjusted. It is preferable to contain 1 type, and it is particularly preferable to contain at least one selected from Y, Er, and Yb.
- the proportion of the grain boundary phase in the insulating substrate 101 is not necessarily limited, but a composition having a small amount of sintering aid and a small proportion of the grain boundary phase is insufficient in the amount of liquid phase during sintering. For this reason, the sinterability is lowered, and there is a tendency that the strength is lowered because minute voids are formed in the grain boundary phase portion.
- the proportion of the grain boundary phase is large, the melting point of the grain boundary phase is lower than that of sialon, so that the heat resistance tends to decrease.
- the content of rare earth elements is 1 to 15% by mass in terms of oxide in the entire raw material when the insulating substrate 101 is produced so that the grain boundary phase is constituted in the insulating substrate 101 at an appropriate ratio. It is preferable to do.
- the silicide in the insulating substrate 101 is contained in order to adjust the coefficient of thermal expansion of the insulating substrate 101. Specifically, it is contained in order to make the thermal expansion coefficient of the insulating substrate 101 close to the thermal expansion coefficient of the heating resistor 102 and to improve durability against repeated temperature rise.
- This silicide is made of at least one silicide selected from Cr, W, Mo, V, and Fe, and is usually contained in the insulating substrate 101 in a granular form. In addition, this silicide is added as an oxide of Cr, W, Mo, V, or Fe, for example, and is generated by being silicided during sintering.
- the content of silicide is preferably 0.1 to 8% by volume in the entire insulating substrate 101.
- the content of silicide is preferably 0.1 to 8% by volume in the entire insulating substrate 101.
- the volume fraction of silicide is obtained by mirror-polishing the cross section of the insulating substrate 101, taking a cross-sectional image with a scanning electron microscope (SEM), calculating the area ratio of the particles by image analysis, and calculating the theoretical volume from the area ratio.
- SEM scanning electron microscope
- the rate can be calculated and calculated in a pseudo manner.
- the heating resistor 102 is mainly composed of a conductive compound composed of at least one selected from Mo silicides, nitrides and carbides, and W silicides, nitrides and carbides. is there.
- a conductive compound composed of at least one selected from Mo silicides, nitrides and carbides, and W silicides, nitrides and carbides.
- heat resistance sufficient for use under a high temperature condition of 1200 ° C. or higher can be obtained.
- the conductive compound WC, WSi 2 , and MoSi 2 are particularly preferable.
- the content of the conductive compound is not necessarily limited, but is preferably 15 to 35% by volume in the entire heating resistor 102.
- the content of the conductive compound is more preferably 20 to 30% by volume in the entire heating resistor 102.
- the heating resistor 102 has ⁇ -sialon or a mixed phase sialon of ⁇ -sialon and ⁇ -sialon as an insulating component.
- the insulating component of the heating resistor 102 is also ⁇ -sialon or a mixed phase sialon of ⁇ -sialon and ⁇ -sialon, so that the sintering behavior and heat shrinkage of both are combined. It is possible to suppress the generation and breakage of the heating resistor 102 at the time of sintering, the separation at the interface between the insulating substrate 101 and the resistor 102, and the durability against repeated temperature rise can be improved. .
- the ratio ( ⁇ ratio) of ⁇ -sialon in the sialon ( ⁇ -sialon and ⁇ -sialon) of the heating resistor 102 is not necessarily limited. However, if the ⁇ ratio is high, the sinterability decreases and the density decreases. 60% or less is preferable because strength and durability against repeated temperature increases are likely to decrease. From the viewpoint of making the strength and durability against repeated heating higher, the ⁇ ratio is preferably 50% or less, more preferably 10% or less, and particularly preferably 5% or less.
- the heating resistor 102 is embedded in the insulating base 101 and does not require oxidation resistance like the insulating base 101, so the ⁇ ratio may be low and is 0%. May be.
- the ⁇ rate in is preferably lower than the ⁇ rate in the insulating substrate 101. Specifically, it is in the range of 60% or less, more preferably in the range of 50% or less, and further preferably in the range of 10% or less as described above. Among them, it is preferable that the ⁇ rate in the insulating substrate 101 is lower.
- the Z value in ⁇ -sialon in the heating resistor 102 is not necessarily limited, but is preferably 0.1 or more from the viewpoint of obtaining sufficient sinterability.
- the amount of solid solution of alumina increases, so that it approaches the properties of alumina and becomes stable, and the sinterability is also good, but the strength of ⁇ -sialon itself decreases, and repeatedly Since the durability with respect to the temperature rise decreases, 1.3 or less is preferable, 1.0 or less is more preferable, and 0.7 or less is particularly preferable.
- the sintering aid added to promote the sintering becomes a liquid phase, and sialon (particle) generation, rearrangement, After contributing to grain growth, it solidifies upon cooling and is produced as a glass or crystalline phase.
- This grain boundary phase also contains at least a rare earth element. Specifically, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb And one or more selected from Lu.
- the proportion of the grain boundary phase in the heating resistor 102 is not necessarily limited, but the content of the rare earth element is the same as that of the raw material for producing the heating resistor 102 as in the viewpoint of the insulating substrate 101. Among them, the content is preferably 1 to 15% by mass in terms of oxide.
- FIG. 2 is an exploded perspective view showing the element molded body 10a that becomes the heater element 10 by firing.
- the element molded body 10a has a resistor molded portion 102a that becomes a heat generating resistor 102 by firing, and an insulating substrate molded portion 101a that becomes an insulating substrate 101 by firing.
- the resistor molding portion 102a is manufactured by using, as the conductive compound powder, a powder composed of at least one selected from Mo silicides, nitrides and carbides, and W silicides, nitrides and carbides, and sialon.
- a powder containing silicon elements (sialon constituent powder) silicon nitride powder, alumina powder, aluminum nitride powder, etc., as sintering aids, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, and Lu selected from one or more rare earth element oxide powders and wet-mixed.
- Suitable examples of the conductive compound powder include WC, WSi 2 and MoSi 2 .
- the oxide powder of 1 type, or 2 or more types of rare earth elements chosen from Sc, Y, Dy, Er, Yb, and Lu is mentioned as a suitable thing.
- the mixing ratio of each raw material powder in the whole raw material powder is not necessarily limited.
- the conductive compound powder is 55 to 70% by mass
- the sialon constituting powder is 25 to 40% by mass
- the rare earth oxide powder is 1 to 15% by mass. preferable.
- Each raw material powder preferably has an average particle size of 5 ⁇ m or less, more preferably 3 ⁇ m or less, and still more preferably 1 ⁇ m or less.
- the slurry-like mixture obtained by wet mixing is dried and granulated by spray drying.
- the powder obtained by this drying is kneaded by adding a binder in a kneading kneader.
- This kneaded material is formed into a three-dimensional U-shape as shown in FIG. 2 by an injection molding machine, and a resistor molding portion 102a that becomes a heating resistor 102 is produced by firing.
- the insulating base molding portion 101a is manufactured by using at least one selected from Cr, W, Mo, V, and Fe as a silicide powder, such as a silicon nitride powder, an alumina powder, and an aluminum nitride powder as a sialon constituent powder.
- a silicide powder such as a silicon nitride powder, an alumina powder, and an aluminum nitride powder as a sialon constituent powder.
- One or two or more rare earth element oxide powders selected from Lu are blended, wet pulverized and mixed, a binder is added, and an insulating base powder is obtained by spray drying.
- the insulating base powder is press-molded using a mold apparatus having a predetermined mold, thereby covering one side surface (for example, the lower side surface in the drawing) of the resistor molding portion 102a as shown in FIG.
- the split insulating base molding part 101a is produced.
- the half-insulated base molding portion 101a is formed with a concave portion 105a having a shape corresponding to the resistor molding portion 102a.
- oxide powders of one or more rare earth elements selected from Sc, Y, Dy, Er, Yb, and Lu are preferable.
- the mixing ratio of each raw material powder in the whole raw material powder is not necessarily limited.
- sialon constituent powder 85 to 97 mass%, silicide powder 0.5 to 5 mass%, rare earth oxide powder 1 to 15 mass % Is preferred.
- Each raw material powder preferably has an average particle size of 5 ⁇ m or less, more preferably 3 ⁇ m or less, and still more preferably 1 ⁇ m or less.
- the above-described half-insulated base molding portion 101a is accommodated in the mold 21, and the resistor molding portion 102a is placed on the concave portion 105a.
- the mold 21 containing the half-split insulating base molding portion 101a is filled with the same insulating base powder as the insulating base powder used for the molding, and press-molded with a pair of punches 22 to obtain the other.
- the half-insulated base molding portion 101a is molded and integrated at the same time, and an element molded body 10a to be the heater element 10 is manufactured by firing.
- the element molded body 10a is calcined at about 600 to 800 ° C. in order to remove the binder component.
- the element molded body 10a subjected to the calcination is subjected to cold isostatic pressing (CIP) as necessary.
- CIP cold isostatic press
- the cold isostatic press (CIP) is performed, for example, by enclosing the element molded body 10a in a rubber tube and applying hydrostatic pressure to the tube by a liquid molding medium such as oil or water.
- the element molded body 10a is fired.
- a normal pressure firing method for firing, a gas pressure firing method, a HIP method, a hot press method, or the like can be applied.
- the atmospheric pressure firing method is very useful because it can be processed in a large amount and is inexpensive.
- firing is performed at 1500 to 1800 ° C. in a non-oxidizing atmosphere of normal pressure of 0.1 MPa, preferably at a nitrogen partial pressure of 0.05 MPa or more.
- the gas pressure firing method is performed at 1500 to 1950 ° C. in a non-oxidizing atmosphere with a gas pressure of 0.1 to 1 MPa, preferably at a nitrogen partial pressure of 0.05 MPa or more.
- HIP method primary firing is performed by normal pressure firing or gas pressure firing, followed by firing at 1450 to 1900 ° C. in a nitrogen atmosphere with a gas pressure of 1 to 200 MPa, preferably with a nitrogen partial pressure of 0.05 MPa or more
- Next firing is performed.
- firing is performed at 1450 to 1900 ° C. under a uniaxial pressure condition of a hot press pressure of 10 to 50 MPa, in a non-oxidizing atmosphere of 0.1 to 1 MPa, preferably at a nitrogen partial pressure of 0.05 MPa or more. It is.
- the ⁇ ratio and Z value in the sialon of the insulating base 101 and the heating resistor 102 can be adjusted by appropriately adjusting the blending ratio of each raw material powder, the firing temperature, and the like within the above ranges.
- the ⁇ ratio can be adjusted mainly by a sintering aid, for example, a rare earth oxide of at least one element selected from Sc, Y, Dy, Er, Yb, and Lu as the sintering aid.
- powder, Al 2 O 3 powder, using an AlN powder can be suitably carried out by adjusting the addition amount.
- the amount of N can be adjusted by the balance of the amount of all rare earth elements. Generally, if the ratio of Al 2 O 3 / AlN is increased, the ⁇ ratio can be decreased, and conversely, if the ratio of Al 2 O 3 / AlN is decreased, the ⁇ ratio can be increased.
- the Z value can be adjusted, for example, by increasing or decreasing the ratio of the content of Al 2 O 3 and AlN in the raw material to be used or the total ratio of Al 2 O 3 and AlN to the entire raw material. Generally, when the ratio of Al 2 O 3 / AlN is increased and the total ratio of Al 2 O 3 and AlN is decreased, the Z value can be decreased, the ratio of Al 2 O 3 / AlN is decreased, and the Al 2 If the total ratio of O 3 and AlN is increased, the Z value can be increased.
- the fired product thus obtained is further polished and finished to a predetermined outer shape, so that the heating resistor 102 is embedded in the insulating substrate 101 and the composition of the insulating substrate 101 and the heating resistor 102.
- the heater element 10 having a predetermined composition can be obtained.
- Examples 1 to 22, Comparative Examples 1 to 5 As the conductive compound powder, one or two kinds selected from WC, WSi 2 , MoSi 2 , and TiN, as the sialon constituting powder, Si 3 N 4 , Al 2 O 3 , and AlN, as the sintering aid, Y 2 O 3, La 2 O 3 , Er 2 O 3, and one or two elements selected from Yb 2 O 3, mixed other SiO 2 as an average particle diameter of 0.5 ⁇ 1 [mu] m, respectively, in a ball mill for 24 hours Wet mixed.
- the composition of each raw material powder is adjusted so that the volume fraction of the conductive compound is 24 to 28% by volume as shown in Table 1.
- Si 3 N 4 , Yb 2 O 3 , Al 2 O 3 , AlN, and SiO 2 powder are used for the preparation of the heating resistor powder of Example 1. It was. Yb 2 O 3 , Al 2 O 3 , AlN, and SiO 2 function as a sintering aid, and sialon is generated by dissolving in Si 3 N 4 during firing. By adding AlN in addition to Al 2 O 3 as the Al component, sialon is easily formed.
- Al 2 O 3 and AlN In order to increase the Z value as in Example 10, a large amount of Al 2 O 3 and AlN (a mass ratio of about 3 to 30 when Si 3 N 4 is defined as 100), Al 2 The O 3 / AlN ratio is preferably blended to about 0.5 to 10.
- AlN In order to set the Z value to 0 as in Comparative Example 1, AlN is not included and the Al component is only Al 2 O 3 or the Al component is zero, and the amount of Al is less than that of Si 3 N 4 (by mass ratio).
- Si 3 N 4 is 100, about 3 or less in terms of Al 2 O 3 ).
- the Al 2 O 3 / AlN ratio may be reduced (2 or less). The ⁇ ratio can be increased as the Al 2 O 3 / AlN ratio is decreased.
- a binder was added to the powder obtained by this drying in a kneading kneader and kneaded for 8 hours. Furthermore, the kneaded product was formed into a three-dimensional U-shape by an injection molding machine, and a resistor molding part that became a heating resistor was produced by firing.
- Si 3 N 4 , Al 2 O 3 , and AlN as insulating base powders
- Cr 2 O 3 , CrSi 2 , WO 3 , WSi 2 , MoO 2 as thermal expansion coefficient adjusting materials (powder for silicide, etc.) 1 or 2 selected from MoSi 2 , V 2 O 5 , VSi 2 , 1 selected from Y 2 O 3 , La 2 O 3 , Er 2 O 3 , and Yb 2 O 3 as a sintering aid.
- a binder was added and a mixed powder was obtained by spray drying.
- the Al component is only Al 2 O 3, and the Al amount is small with respect to the entire raw material (3 wt% or less in terms of Al 2 O 3). Degree).
- a large amount of Al 2 O 3 and AlN total amount of about 10 to 20 wt%) and an Al 2 O 3 / AlN ratio of about 0.5 to 10 are used. It is good to mix with.
- the Al 2 O 3 / AlN ratio is increased (about 1 to 10).
- the Al 2 O 3 / AlN ratio is decreased (2 or less). The ⁇ ratio can be increased as the Al 2 O 3 / AlN ratio is decreased.
- the mixed powder was fitted with a pair of insulating base molding parts so as to accommodate the resistor molding part, and then accommodated in a mold and press-molded with a pair of punches to obtain an element molding. Further, the element molded body was calcined at 600 ° C. in a nitrogen atmosphere in order to remove the binder component, and further pressurized by a cold isostatic press (CIP) at a pressure of 20 to 150 MPa. .
- CIP cold isostatic press
- the element compact subjected to cold isostatic pressing (CIP) was fired at 1750 ° C. for 2 hours in a 0.1 MPa nitrogen atmosphere. In this way, a heater element in which a heating resistor was embedded in an insulating substrate was manufactured.
- CIP cold isostatic pressing
- the constituent phases were identified, and the ⁇ rate and Z value were determined.
- the constituent phases were identified by X-ray diffraction measurement, and the ⁇ rate and Z value were determined by the methods already described.
- the volume fraction of silicide in the insulating substrate and the volume fraction of conductive compound in the heating resistor were determined. Each volume fraction is mirror-polished on the cross section of the heater element, the cross-sectional image is taken in by a scanning electron microscope (SEM), and is calculated as an area ratio of particles by image analysis. From this area ratio, the theoretical volume ratio is simulated. Calculated. The measurement results are shown in Table 1 together with the manufactured samples.
- the insulating substrate of Example 1 Yb 2 O 3 to 5.5wt%, Al 2 O 3 and 4.5 wt%, AlN and 5.5 wt%, WO 3 and 1.8 wt%, the balance being Si 3 N
- the raw material mixed powder (insulating base powder) was 4.
- the ⁇ ratio was 0.15 and the Z value was 0.7.
- the insulating substrate of Example 3 Yb 2 O 3 and 5.5 wt%, Al 2 O 3 to 11 wt%, AlN and 5.5 wt%, WO 3 and 1.8 wt%, and the balance Si 3 N 4
- the ⁇ ratio is 0, and the Z value is 1.
- the ⁇ ratio and the Z value can be adjusted by appropriately changing the blending ratio of Al 2 O 3 and AlN.
- the fracture toughness value of the insulating substrate was measured according to JIS®R-1607.
- the strength of the heater element a three-point bending strength was measured according to JISJR 1601. The span at this time was 12 mm, and the crosshead speed was 0.5 mm / min.
- the power consumption measured the power consumption at 1200 degreeC saturation.
- the rapid temperature rising property was measured by applying a DC voltage of 11 V and measuring the time until the temperature of the tip of the heater element reached 1000 ° C.
- the continuous energization durability was a continuous energization test in which the temperature was raised so that the maximum surface temperature was 1250 ° C or 1300 ° C. And after energizing for 1000 hours, resistance value was first measured and resistance value change before and after a test was measured. After measuring the resistance value, the heater element is cut along the axial direction, mirror-polished, and the presence or absence of migration (migration) of the sintering aid component (rare earth element, aluminum, etc.) in the vicinity of the heating resistor is detected by EPMA. Observed. In this case, when there was no resistance change and no migration, the evaluation of “ ⁇ ” was made. When the resistance change was not so much, the evaluation of “ ⁇ ” was made when there was migration, and the resistance value was 10%. When it increased more and there was migration, "x" evaluation was carried out.
- Oxidation resistance was determined by measuring the weight before and after standing in a heating furnace in an air atmosphere at 1250 ° C. or 1300 ° C. for 50 hours, and obtaining an oxidation increase value.
- the oxidation increase value is a value obtained by dividing the difference between the weight after standing and the weight before standing by the surface area, 0.3 mg / cm 2 or less at 1250 ° C. and 0.4 mg / cm at 1300 ° C. When it was cm 2 or less, it was evaluated as “ ⁇ ” as being excellent in oxidation resistance, and when exceeding that, it was evaluated as “surface oxidation” as the oxidation proceeded.
- the ON / OFF durability is a process in which a voltage at a temperature rising rate reaching 1000 ° C. in 2 seconds is applied, the voltage is allowed to reach the maximum temperature of 1250 ° C., and then the voltage application is stopped and the fan is cooled for 30 seconds.
- the number of cycles in which the resistance value changed by 10% or more relative to the resistance value before the start of the test was measured.
- “ ⁇ ” indicates up to 100,000 cycles
- “ ⁇ ” indicates up to 20,000 cycles
- “ ⁇ ” indicates up to 500 cycles
- the resistance value change is less than 10%.
- "x" shows having disconnected by less than 500 cycles.
- the heater element of Comparative Example 1 in which the insulating base and the heating resistor are silicon nitride as the main phase consumes a large amount of power is inferior in rapid temperature rise, and has oxidation resistance. It turns out that it is not enough.
- the heater element of Comparative Example 2 in which the insulating base does not have a predetermined silicide has insufficient ON / OFF durability because the thermal expansion coefficients of the insulating base and the heating resistor are different.
- the heater element of Comparative Example 4 in which the conductive compound of the heating resistor is TiN, and the heater element of Comparative Example 5 that does not contain a rare earth element It can be seen that the heating resistor is cut or not sufficiently densified during firing.
- the heater element of the example has low power consumption and good rapid temperature rise.
- the sinterability is also good, and it can be seen that the generation and breakage of the heating resistor during firing and peeling at the interface between the insulating substrate and the heating resistor are suppressed.
- the ⁇ ratio of the insulating substrate and the heating resistor is preferably 0.5 or less.
- the ⁇ ratio of the insulating substrate is preferably larger than the ⁇ rate of the heating resistor.
- the Z value of the insulating substrate is preferably 1 or less. Recognize. Similarly, in the case where the Z value of the heating resistor exceeds 1 as in the heater element of Example 10, the strength of the heating resistor is lowered, and as a result, the ON / OFF durability tends to be lowered. It can be seen that the Z value is preferably 1 or less.
- the silicide may be a silicide other than W, and may contain two or more silicides.
- Example 23 to 29 Heater elements having different ⁇ ratios of the insulating bases as shown in Table 3 were manufactured by a manufacturing method basically similar to the manufacturing method in the above-described embodiment. The ⁇ ratio was adjusted by adjusting the composition of the raw material powder and the firing conditions.
- Example 26 is the same as Example 1
- Example 28 is the same as Example 6
- Example 29 is the same as Example 7.
- the obtained heater element was evaluated for the fracture toughness value of the insulating substrate, the strength of the heater element, continuous conduction durability (oxidation resistance), and ONOFF durability.
- the continuous energization durability (oxidation resistance) was evaluated by changing the temperature to 1350 ° C.
- the ONOFF durability was evaluated by changing the maximum temperature to 1300 ° C. That is, a process of applying a voltage at a temperature rising rate reaching 1000 ° C. in 2 seconds, reaching the maximum temperature 1300 ° C. with the voltage as it is, and then stopping the voltage application and cooling the fan for 30 seconds is defined as one cycle. .
- the results are shown in Table 4.
- the ⁇ ratio of the insulating substrate is 2% or more, the ratio of the grain boundary phase in the insulating substrate is reduced, so that the oxidation resistance can be ensured.
- the ⁇ ratio of the insulating substrate is 30% or less, a dense sintered body can be obtained, and the strength and durability against repeated temperature rise can be ensured.
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Abstract
Description
図1は、本発明のセラミックヒータ素子(以下、単にヒータ素子という)を有するグロープラグの一例を示したものである。ここで、図1(a)は、グロープラグ全体の縦断面図であり、図1(b)は、そのセラミックヒータ素子部分の断面図である。
絶縁基体101は、上記したように、β-サイアロンまたはβ-サイアロンとα-サイアロンとの混相サイアロンを主相とするものである。なお、主相とは、構成相中、最も質量の多い相を意味する。一方、発熱抵抗体102もまた、同様のサイアロンを有して構成される。
図2は、焼成によりヒータ素子10となる素子成形体10aを示す分解斜視図である。素子成形体10aは、焼成により発熱抵抗体102となる抵抗体成形部102aと、焼成により絶縁基体101となる絶縁基体成形部101aとを有する。
導電性化合物粉末として、WC、WSi2、MoSi2、およびTiNから選ばれる1種または2種、サイアロン構成粉末として、Si3N4、Al2O3、およびAlN、焼結助剤として、Y2O3、La2O3、Er2O3、およびYb2O3から選ばれる1種または2種、その他にSiO2をそれぞれ平均粒径0.5~1μmとして配合し、ボールミルで24時間湿式混合した。なお、それぞれの原料粉末の組成は、表1に示すように導電性化合物の体積分率が24~28体積%となるように調整している。
上記実施例における製造方法と基本的に同様の製造方法により、表3に示すような絶縁基体のα率が異なるヒータ素子を製造した。α率の調整は、原料粉末の組成および焼成条件の調整により行った。なお、実施例26は実施例1と同一であり、実施例28は実施例6と同一であり、実施例29は実施例7と同一である。
2…セラミックヒータ
3…主体金具
10…セラミックヒータ素子(10a…素子成形体)
11…金属外筒
101…絶縁基体(101a…絶縁基体成形部)
102…発熱抵抗体(102a…抵抗体成形部)
Claims (7)
- 絶縁基体と、前記絶縁基体に埋設される発熱抵抗体とを有するセラミックヒータ素子であって、
前記絶縁基体は、β-サイアロンまたはβ-サイアロンとα-サイアロンとの混相サイアロンを主相とし、希土類元素を含有する粒界相と、Cr、W、Mo、V、およびFeの中から選ばれる少なくとも1種の珪化物とを有し、
前記発熱抵抗体は、Moの珪化物、窒化物、および炭化物、ならびにWの珪化物、窒化物、および炭化物の中から選ばれる少なくとも1種からなる導電性化合物を主相とし、β-サイアロンまたはβ-サイアロンとα-サイアロンとの混相サイアロンと、希土類元素を含有する粒界相とを有することを特徴とするセラミックヒータ素子。 - 前記絶縁基体および前記発熱抵抗体のサイアロン相におけるα率は50%以下であることを特徴とする請求項1記載のセラミックヒータ素子。
- 前記絶縁基体のサイアロン相におけるα率は2%以上30%以下であることを特徴とする請求項1または2記載のセラミックヒータ素子。
- 前記絶縁基体および前記発熱抵抗体のβ-サイアロンのZ値は0を超え1以下であることを特徴とする請求項1乃至3のいずれか1項記載のセラミックヒータ素子。
- 前記絶縁基体に含まれる希土類元素は、Y、Er、およびYbから選ばれる少なくとも1種を含み、前記発熱抵抗体に含まれる希土類元素は、Y、Er、およびYbから選ばれる少なくとも1種を含むことを特徴とする請求項1乃至4のいずれか1項記載のセラミックヒータ素子。
- セラミックヒータ素子と、前記セラミックヒータ素子を先端部が突出するように内部に保持する金属外筒とを有するセラミックヒータであって、
前記セラミックヒータ素子が請求項1乃至5のいずれか1項記載のセラミックヒータ素子であることを特徴とするセラミックヒータ。 - セラミックヒータと、前記セラミックヒータの後端部を内部に保持する筒状の主体金具とを備えるグロープラグであって、
前記セラミックヒータが請求項6記載のセラミックヒータであることを特徴とするグロープラグ。
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JP2012511080A JP5342694B2 (ja) | 2010-12-02 | 2011-11-29 | セラミックヒータ素子、セラミックヒータ、およびグロープラグ |
US13/878,722 US9247585B2 (en) | 2010-12-02 | 2011-11-29 | Ceramic heater element, ceramic heater, and glow plug |
EP11844018.9A EP2648475B1 (en) | 2010-12-02 | 2011-11-29 | Ceramic heater element, ceramic heater, and glow plug |
KR1020137017182A KR101470781B1 (ko) | 2010-12-02 | 2011-11-29 | 세라믹 히터 소자, 세라믹 히터 및 글로 플러그 |
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JP2015153605A (ja) * | 2014-02-14 | 2015-08-24 | 日本特殊陶業株式会社 | セラミックヒータ素子、セラミックヒータおよびグロープラグ |
JP2015197990A (ja) * | 2014-04-01 | 2015-11-09 | 日本特殊陶業株式会社 | セラミックヒータ |
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RU188873U1 (ru) * | 2018-12-19 | 2019-04-25 | федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский ядерный университет "МИФИ" (НИЯУ МИФИ) | Устройство для электроимпульсного прессования порошковых материалов |
RU196265U1 (ru) * | 2019-12-06 | 2020-02-21 | федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский ядерный университет "МИФИ" (НИЯУ МИФИ) | Устройство для электроимпульсного прессования порошковых материалов |
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JP2015153606A (ja) * | 2014-02-14 | 2015-08-24 | 日本特殊陶業株式会社 | セラミックヒータ素子、セラミックヒータおよびグロープラグ |
JP2015153605A (ja) * | 2014-02-14 | 2015-08-24 | 日本特殊陶業株式会社 | セラミックヒータ素子、セラミックヒータおよびグロープラグ |
JP2015197990A (ja) * | 2014-04-01 | 2015-11-09 | 日本特殊陶業株式会社 | セラミックヒータ |
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KR101470781B1 (ko) | 2014-12-08 |
JP5342694B2 (ja) | 2013-11-13 |
EP2648475A1 (en) | 2013-10-09 |
US20130213954A1 (en) | 2013-08-22 |
US9247585B2 (en) | 2016-01-26 |
KR20130094846A (ko) | 2013-08-26 |
EP2648475B1 (en) | 2018-10-17 |
JPWO2012073476A1 (ja) | 2014-05-19 |
EP2648475A4 (en) | 2017-05-17 |
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