JP2017197642A - Fluorescent zirconia material and device for detecting beam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent zirconia material capable of being used repeatedly because of little fracture such as cracks even in such an environment as exposed to a high temperature repeatedly, and a device for detecting a beam.SOLUTION: The fluorescent zirconia material of the present disclosure is a zirconium oxide ceramic containing at least any of neodymium, samarium, terbium, holmium, erbium, and thulium, and a main crystal structure in a zirconium oxide crystal is a cubic crystal. The device for detecting a beam of the present disclosure comprises the fluorescent zirconia material.SELECTED DRAWING: None

Description

  The present disclosure relates to fluorescent zirconia materials and beam detection devices.

  In order to provide a traceability function in replacement parts for frames and machinery used in dental prostheses, a fluorescent zirconia material that contains a fluorescent component and emits fluorescence when excited by light of a predetermined wavelength is used. It has been.

  For example, Patent Document 1 includes at least one element of Pr, Sm, Eu, Ga, Gd, Tm, Nd, Dy, Tb, and Er as a fluorescent component and zirconium oxide itself. A fluorescent zirconia material that emits fluorescence when excited with light having a predetermined wavelength has been proposed. This fluorescent zirconia material describes that the content of yttrium oxide as a stabilizer is 1.5 to 6.0% by mass.

Japanese Patent No. 5501642

  There are not less monoclinic crystals in partially stabilized zirconia in which the content of yttrium oxide as a stabilizer is 1.5 to 6.0% by mass. When a fluorescent zirconia material made of such partially stabilized zirconia is used in an environment where it is repeatedly exposed to high temperatures, the surface of the fluorescent zirconia material is cracked and cannot be used for a long period of time. was there.

  The present disclosure provides a fluorescent zirconia material characterized in that it is a zirconium oxide ceramic containing at least one of neodymium, samarium, terbium, holmium, erbium and thulium, and the crystal structure of the zirconium oxide crystal is cubic. To do. Moreover, the apparatus for beam detection provided with the said fluorescent zirconia material is provided.

  The beam detection apparatus including the fluorescent zirconia material and the fluorescent zirconia material of the present disclosure can be repeatedly used even in an environment where they are repeatedly exposed to a high temperature with little damage such as cracks.

  Hereinafter, an embodiment of the fluorescent zirconia of the present disclosure and an embodiment of the beam detection apparatus of the present disclosure will be described.

  The fluorescent zirconia material of this embodiment is a zirconium oxide ceramic containing at least one of neodymium, samarium, terbium, holmium, erbium, and thulium, and the crystal structure of the zirconium oxide crystal is cubic. The fluorescent zirconia material of the present embodiment has a cubic crystal structure in the zirconium oxide crystal, so there is no strength deterioration due to phase transformation, and there is little damage such as cracks even in an environment where it is repeatedly exposed to high temperatures, and it is used repeatedly. can do. The fluorescent zirconia material of this embodiment is fully stabilized zirconia (FSZ).

  And the fluorescent zirconia material of this embodiment contains yttrium oxide as a stabilizer, and content of yttrium oxide is 13 mass% or more and 20 mass% or less. In order to make the crystal structure of the zirconium oxide crystal cubic, the stabilizer includes yttrium oxide, calcium oxide, magnesium oxide, cerium oxide, etc. Among these stabilizers, yttrium oxide has an ionic radius of yttrium, Since it is closest to the ionic radius of zirconium, it is most easily dissolved in zirconium oxide ceramics, and can stabilize the crystal phase and be sintered at a low temperature. Further, when the content of yttrium oxide is 13% by mass or more, the crystal structure of zirconium oxide at a high temperature is stabilized. On the other hand, when the content of yttrium oxide is 20% by mass or less, yttrium oxide is completely dissolved in zirconium oxide. For this reason, the possibility that yttrium oxide is generated by reaction with other impurities and a composite oxide having low durability when exposed to high temperatures is reduced. The impurities in the present embodiment are, for example, titanium oxide, iron oxide, sodium oxide, potassium oxide, and the like.

In addition, the zirconium oxide ceramic in this embodiment occupies 75 mass% or more of the value which converted zirconium (Zr) into zirconium oxide (ZrO ₂ ) out of the total 100 mass% of the components constituting the ceramic. is there. In addition, what is necessary is just to identify using a X-ray-diffraction apparatus (XRD) about whether it is ceramics containing a zirconium oxide.

  The content of each component constituting the fluorescent zirconia material may be converted into an oxide by measuring the content of the metal element using an ICP (Inductively Coupled Plasma) emission spectroscopic analyzer (ICP).

Moreover, the fluorescent zirconia material of this embodiment is, for example, 0.5% by mass or more and 2% by mass in terms of oxide (Sm ₂ O ₃ ) in terms of oxide (Sm ₂ O ₃ ) in a total of 100% by mass of the components constituting the fluorescent zirconia material. Includes: When a fluorescent zirconia material containing 1% by mass of samarium in terms of oxide is irradiated with beams having wavelengths of 213 nm, 265 nm, and 355 nm, an orange so-called warm-colored fluorescent color is emitted.

Another example of the fluorescent zirconia material according to the present embodiment is an oxide (Nd ₂ O _{3) of} neodymium, terbium, holmium, erbium, or thulium out of a total of 100% by mass of the components constituting the fluorescent zirconia material. , Tb ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ ), for example, 0.5% by mass or more and 2% by mass or less. When a fluorescent zirconia material containing 1% by mass of neodymium, terbium, holmium, erbium, or thulium, respectively, is converted into an oxide, irradiation with beams having wavelengths of 213 nm, 265 nm, and 355 nm is a so-called cold system such as white, green, or blue. Emits a fluorescent color.

  The fluorescent zirconia material of the present embodiment preferably has a porosity of 1.5% by volume or less, and this porosity can be determined according to the Archimedes method. The fluorescent zirconia material is, for example, a disk-shaped body having an outer diameter of 20 mm to 40 mm and a thickness of 0.1 mm to 0.4 mm.

  Next, the manufacturing method of the fluorescent zirconia material of this embodiment is demonstrated. The content of each of zirconium oxide and yttrium oxide is a predetermined mass ratio, for example, the content of yttrium oxide is 13% by mass or more and 20% by mass or less in 100% by mass of the components constituting the zirconium oxide ceramics. Then, an aqueous solution of a zirconium compound and an aqueous solution of an yttrium compound are mixed. As such a zirconium compound, for example, zirconium oxychloride can be used, and as the yttrium compound, for example, yttrium oxychloride can be used.

  Then, after preparing a slurry using the coprecipitation method which obtains a hydrate by hydrolysis, it spin-dry | dehydrates, dries, and calcines at 500 degreeC-1200 degreeC, and obtains calcined powder. Then, the calcined powder is pulverized with a ball mill or the like by a wet method, and dried to obtain a stabilized dry powder.

The oxides of neodymium, samarium, terbium, holmium, erbium, and thulium are converted into oxides when the calcined powder is pulverized. For example, it may be added so as to contain 0.5 mass% or more and 2 mass% or less. In addition, if the average particle diameter (D ₅₀ ) of the zirconium oxide powder stabilized by a stabilizer such as yttrium oxide is 0.05 μm or more and 0.2 μm or less, the crystal of zirconium oxide becomes fine. The mechanical strength and fracture toughness of the porous zirconia material can be increased. In particular, the average particle diameter (D ₅₀ ) is more preferably 0.05 μm or more and 0.1 μm or less.

Next, a granulated powder having an average particle size (D ₅₀ ) of, for example, 40 μm or more and 55 μm or less can be obtained by adding silica sol and an organic binder to the dry powder and spray drying.

  Then, the obtained granulated powder is filled in a mold, and a molded body can be obtained by a method such as press molding or CIP molding (rubber press).

  Finally, the beam detection member of the present embodiment can be obtained by firing the compact in an air atmosphere at a holding temperature of 1400 ° C. to 1500 ° C. and a holding time of 1 hour to 3 hours.

  In the fluorescent zirconia material of the present embodiment, fluorescent spectra having different shapes appear depending on the wavelength of light to be irradiated. The fluorescent zirconia of this embodiment can be used, for example, in a beam detection device for detecting a beam including a specific wavelength. The beam detector includes, for example, the fluorescent zirconia material, a light receiving unit that receives fluorescence emitted when the fluorescent zirconia material is irradiated with a beam, and generates a signal corresponding to the received light, and the light receiving unit. It is only necessary to have an analysis unit that analyzes the signal generated in (1). The light receiving unit includes, for example, a plurality of types of wavelength filters and photoelectric conversion elements, and generates an electrical signal having an intensity corresponding to the light intensity for each of a plurality of types of wavelengths included in the received light. The analysis unit analyzes the spectrum of the wavelength received by the light receiving unit by processing each electrical signal.

  For example, the fluorescent zirconia is irradiated with a beam whose wavelength distribution is unknown, the fluorescence emitted from the fluorescent zirconia is received by the light receiving unit, and the wavelength spectrum of the fluorescence is examined by the analyzing unit. It is possible to detect whether light of each wavelength component of 265 nm and 355 nm is included. Alternatively, by analyzing in detail the wavelength spectrum of the fluorescence emitted from the fluorescent zirconia, the wavelength distribution of the beam irradiated to the fluorescent zirconia can be derived in some detail.

  The fluorescent zirconia of this embodiment can be used repeatedly even in an environment where it is repeatedly exposed to high temperatures with little damage such as cracks. For example, when the fluorescent zirconia material of the present embodiment is arranged inside a chamber in a semiconductor manufacturing apparatus where plasma is generated and the fluorescence according to the light of the plasma is examined, the damage due to the temperature of the plasma is small, It can be used with stable performance over a wide range.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the above-mentioned embodiment.

Claims (3)

  A fluorescent zirconia material, characterized in that it is a zirconium oxide ceramic containing at least one of neodymium, samarium, terbium, holmium, erbium and thulium, and the crystal structure of the zirconium oxide crystal is cubic.   2. The fluorescent zirconia according to claim 1, wherein the content of yttrium oxide is 13% by mass or more and 20% by mass or less in 100% by mass of the component that contains yttrium oxide and constitutes the zirconium oxide ceramics. Wood.   A beam detection apparatus comprising the fluorescent zirconia material according to claim 1.