WO2020235547A1 - Ni基自溶性合金、Ni基自溶性合金を用いたガラス製造用部材、ガラス製造用部材を用いた金型及びガラス塊搬送用部材 - Google Patents
Ni基自溶性合金、Ni基自溶性合金を用いたガラス製造用部材、ガラス製造用部材を用いた金型及びガラス塊搬送用部材 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B7/00—Distributors for the molten glass; Means for taking-off charges of molten glass; Producing the gob, e.g. controlling the gob shape, weight or delivery tact
- C03B7/14—Transferring molten glass or gobs to glass blowing or pressing machines
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B7/00—Distributors for the molten glass; Means for taking-off charges of molten glass; Producing the gob, e.g. controlling the gob shape, weight or delivery tact
- C03B7/14—Transferring molten glass or gobs to glass blowing or pressing machines
- C03B7/16—Transferring molten glass or gobs to glass blowing or pressing machines using deflector chutes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B9/00—Blowing glass; Production of hollow glass articles
- C03B9/30—Details of blowing glass; Use of materials for the moulds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B9/00—Blowing glass; Production of hollow glass articles
- C03B9/30—Details of blowing glass; Use of materials for the moulds
- C03B9/48—Use of materials for the moulds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
Definitions
- the present invention relates to a Ni (nickel) -based self-soluble alloy used for a glass manufacturing member for transporting or molding glass, a glass manufacturing member using a Ni-based self-soluble alloy, a mold using a glass manufacturing member, and a mold.
- the present invention relates to a member for transporting a glass gob.
- Patent Document 2 As a member for manufacturing glass having excellent heat resistance and wear resistance, an alloy containing a very small amount of B (boron) has been proposed (for example, Patent Document 2).
- Ni 40 to 70% by mass
- Cr (chromium) 5 to 40%
- B 1 to 6%
- Si silicon
- C carbon
- Those containing ⁇ 2.0%, Fe (iron): 1-10%, W (tungsten): 1-20%, Cu (copper): 0.8-5% have been proposed (for example, Patent Documents). 3).
- the properties required of a glass manufacturing member that comes into contact with a molten glass block in the molding process of a glass product are that it is difficult to adhere to the molten glass block and that there are no holes or the like (pinholes, etc.) on the surface of the member unless it is intentionally provided.
- the present invention has a Ni-based self-soluble alloy used for a glass manufacturing member, a glass manufacturing member using a Ni-based self-soluble alloy, which has high wear resistance and low adhesiveness to molten glass.
- An object of the present invention is to provide a mold and a member for transporting a glass ingot using a member for manufacturing glass.
- a Ni-based alloy characterized by containing 0% by mass or more and 1.5% by mass or less of B, hard particles, and Si, and a glass manufacturing member using the alloy. ..
- Another aspect of the present invention provides a mold and a glass ingot transporting member using a glass manufacturing member forming a portion in contact with molten glass in a glass molding process using the alloy.
- Ni-based self-soluble alloy of the present invention is difficult to adhere to molten glass even when its surface is in a high temperature region. Therefore, when the alloy is applied to all or a part of the glass manufacturing member, the friction when it comes into contact with the molten glass is suppressed, and as a result, the swabbing frequency can be reduced and the product yield can be improved by suppressing product defects.
- Graphs showing the adhesion ratio of molten glass to the sample surface temperature for Examples 35 to 39 A graph showing the adhesion ratio of the molten glass block to the sample surface temperature for Example 40.
- For Example 45 a graph showing the adhesion ratio of the molten glass block to the sample surface temperature.
- Example 48 a graph showing the adhesion ratio of the molten glass block to the sample surface temperature.
- the greatest feature of the present invention is that it has found an alloy composition that does not adhere to molten glass even in a high temperature region by blending a predetermined amount of B or not blending B. According to the present invention, the slipperiness of the molten glass gob on the surface of a Ni-based self-soluble alloy can be improved.
- FIG. 3 is a cross-sectional electron microscope image of the interface where the Ni-based self-soluble alloy (Example 4) of the present invention and the molten glass gob are adhered.
- a molten glass adhesion evaluation test device FIG. 2 described later was used, and molten glass at 1050 ° C. was dropped on the surface of each sample 20 heated to 750 ° C., and then the sample 20 and the sample 20 and the sample 20 were dropped.
- the molten glass is cooled, the glass is fixed to the surface of the sample 20, the surface of the sample 20 and the glass are covered with a resin, and then the sample, the glass and the resin are cut at a plane orthogonal to the surface of the sample to expose the cross section. I let you.
- the exposed cross section was adjusted to be smooth by the ion milling method. From the cross-sectional image of FIG. 3, the oxide film formed on the surface of the base material of the Ni-based self-soluble alloy has a gap with the base material. From this, the following can be considered. As schematically shown in FIG.
- the metal oxide film 15 formed on the surface of the metal material 14 made of the Ni-based self-soluble alloy of the present invention is easily peeled off from the base material (metal material 14) together with the molten glass block 16. Conceivable. Although the clear reason is not clear, it is presumed that the oxide film of the Ni-based self-soluble alloy of the present invention is more easily peeled off by containing the metals of Groups 4, 5 and 6 of the periodic table. Since the oxide films of the metals of Groups 4, 5 and 6 of the Periodic Table have different coefficients of thermal expansion with respect to the Ni-based self-soluble alloy, it is easy to peel off from the Ni-based self-soluble alloy when the temperature rises. Conceivable. Therefore, as shown in FIGS.
- the metal oxide films 15 of Groups 4, 5 and 6 of the Periodic Table are adsorbed on the molten glass block 16 when they come into contact with the high temperature molten glass block 16. It is peeled off from the metal material 14 (base material) made of a Ni-based self-soluble alloy. It is considered that this makes it possible to improve the slipperiness of the Ni-based self-soluble alloy with respect to the glass gob. Further, after the oxide film is peeled off, the oxide film is rapidly regenerated, that is, the state shown in FIG. 1 (C) is quickly returned to the state shown in FIG. 1 (A), whereby the Ni-based self-soluble alloy is made of molten glass. It is considered that high slipperiness to the mass is exhibited for a long period of time.
- Ni has lower adhesiveness to glass than other metal materials.
- the Ni alloy to which B is added may have high adhesiveness to the molten glass gob, that is, the slipperiness of the molten glass gob on the surface of the metal material may be deteriorated.
- the reason for this phenomenon is not clear, but B in the Ni alloy or B 2 O 3 formed on the surface of the Ni alloy in a high temperature environment adheres to the base metal of the Ni alloy oxide.
- the above-mentioned peeling phenomenon of the oxide film is suppressed, and as a result, it adheres firmly to the Ni alloy surface and has poor slipperiness. Etc. can be considered.
- the glass manufacturing member includes a glass molding member and a glass transporting member.
- log ⁇ is the common logarithm.
- the blending amount of the components contained in the Ni-based self-soluble alloy according to the present embodiment is preferably in the following range.
- the glass may be, for example, soda-lime glass, borosilicate glass, lead glass or the like. Further, the glass manufacturing member can be said to be a member for transporting or molding glass at 400 ° C. or higher and 1400 ° C. or lower.
- B boron
- B is 0% by mass or more and 1.5% by mass or less.
- B is 0% by mass or more and 1.1% by mass or less, more preferably 0% by mass or more and less than 1.0% by mass, further preferably 0% by mass or more and less than 0.75% by mass, still more preferably 0% by mass or more and 0. It is preferably less than 5.5% by mass.
- B is more than 0% by mass and less than 1.0% by mass, more preferably more than 0% by mass and less than 0.75% by mass, still more preferably more than 0% by mass and less than 0.5% by mass. ..
- the Ni-based self-soluble alloy may not contain B.
- the Ni-based self-soluble alloy according to the present embodiment contains Si (silicon) in an amount of 0% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and less than 7.5% by mass.
- B and Si are flux components, and the larger the content, the better the self-solubility of the Ni-based self-soluble alloy.
- B and Si form B 2 O 3 and SiO 2 oxide films on the surface of the Ni-based self-soluble alloy. As described above, B 2 O 3 can be a factor for enhancing the adhesiveness with the molten glass. Therefore, it is preferable that the Ni-based self-soluble alloy according to the present embodiment has a small B content.
- the hard particles include carbides, nitrides, oxides, and so-called cermet materials obtained by combining them with a metal material.
- the Ni-based self-soluble alloy according to this embodiment contains at least one of carbides, nitrides, oxides and cermets as hard particles.
- the content of the hard particles is larger than 0% by mass and contains 50% by mass or less, preferably 5% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content of the hard particles is too small, wear resistance cannot be obtained and the particles cannot be used at an early stage, and if the content is too large, it becomes difficult to perform cutting when manufacturing the member.
- Carbide as hard particles comprise any one of a carbide of the periodic table 4, 5 and 6 group elements, for example, TiC (titanium carbide), ZrC (zirconium carbide), HfC (hafnium carbide), VC or V 2 C (Vanadium Carbide), NbC (Niob Carbide), TaC (Tantalum Carbide), Cr 3 C 2 , Cr 7 C 3 or Cr 23 C 6 (Chromium Carbide), Mo 2 C (Molybdenum Carbide), WC or W 2 C (Tungsten carbide) and the like are included.
- the carbide as the hard particles may be silicon carbide.
- the oxide as hard particles may contain an oxide of at least one metal selected from lanthanoids.
- the oxide of at least one metal selected from the lanthanoids may be cerium oxide.
- the cermet may contain a carbide of any one of the elements of Groups 4, 5 and 6 of the Periodic Table.
- the cermet particles obtained by combining the carbide and the metal material are preferably, but are not limited to, WC (WC-12% Co) containing 12% by mass of Co (cobalt) as a binder.
- the above hard particles are dispersed in the Ni-based self-soluble alloy of the base material, improve the wear resistance of the alloy, and exhibit long-term durability when used as a member for glass production.
- the Ni-based self-soluble alloy may contain at least one element selected from the Group 15 elements of the periodic table. It is preferable that at least one element selected from the Group 15 elements of the periodic table is contained in an amount of 0% by mass or more and 15% by mass or less. At least one element selected from the Group 15 elements of the Periodic Table may contain P.
- the Ni-based self-soluble alloy according to this embodiment may contain P (phosphorus).
- P is 0% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less.
- the Ni-based self-soluble alloy according to the present embodiment may contain at least one metal selected from the elements of Groups 4, 5 and 6 of the periodic table.
- the metal is preferably 0% by mass or more and 30% by mass or less, and preferably 2.5% by mass or more and 30% by mass or less.
- the metal is preferably Cr (chromium), and Cr is preferably 2.5% by mass or more and 30% by mass or less.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 3 elements.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 3 elements in an amount of 0% by mass or more and 10% by mass or less. At least one metal selected from the Group 3 elements may be Y.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 7 elements.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 7 elements in an amount of 0% by mass or more and 10% by mass or less. At least one metal selected from the Group 7 elements may be Mn or Re.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 8 elements.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 8 elements in an amount of 0% by mass or more and 30% by mass or less. At least one metal selected from the Group 8 elements is preferably Fe.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 11 elements.
- the Ni-based self-soluble alloy may contain at least one metal selected from Group 11 elements in an amount of 0% by mass or more and 10% by mass or less. At least one metal selected from the Group 11 elements may be Cu or Ag.
- the Ni-based self-soluble alloy according to the present embodiment contains 3.5% by mass or more and 97.5% by mass or less of Ni as a residue of the above components, and may contain a very small amount of impurities unavoidable in the manufacturing process.
- the metal component excluding the hard particles in the Ni-based self-soluble alloy according to the present embodiment may be prepared in any way as long as it has a predetermined composition.
- the Ni-based self-soluble alloy may be formed by, for example, melt-mixing a metal containing a constituent element and an inorganic compound and then solidifying the alloy, or simply mixing fine particles of the metal and the inorganic compound containing the constituent element.
- Sintering or casting can be considered as a method for producing a member for glass production using the Ni-based self-soluble alloy of the present invention, but the method is not limited thereto.
- thermal spraying, plating, clad, and laminating are performed on the contact surface between the mold formed of a metal such as iron and the molten glass ingot of the member for conveying the molten glass ingot. It may be formed by coating a film made of a Ni-based self-soluble alloy by molding, welding, or the like. Further, by performing a fusing treatment (remelting treatment) after forming the film, the pores formed in the film can be closed and the adhesion between the base material and the film can be improved.
- a fusing treatment remelting treatment
- the glass manufacturing member is a mold 42 for forming a glass bottle for molding a glass bottle from molten glass, or a molten glass ingot (gob) supplied from the molten glass tank 43.
- a glass ingot transporting member 44 for transporting to.
- the mold 42 includes a rough mold for molding a parison from a molten glass block, a baffle, a mouth mold, a plunger and a finishing mold for molding a glass bottle from the parison.
- the glass ingot transporting member 44 includes a shooter, a gutter, and the like for transporting the gob to a rough mold.
- the glass gob transport member 44 includes a scoop 44A, a trough 44B, and a deflector 44C.
- the mold 42 and the glass gob transporting member 44 may be entirely formed of a Ni-based self-soluble alloy, or only the surface in contact with the glass gob may be formed of a Ni-based self-soluble alloy as a film.
- the molten glass when 0.3 g of molten glass heated to 1000 ° C. is dropped onto the plate-shaped Ni-based self-soluble alloy heated to 480 ° C. and inclined 70 degrees with respect to a horizontal plane, the molten glass is formed. It has the property of sliding down without adhering to a Ni-based self-soluble alloy.
- the glass manufacturing member includes, for example, a press molding die, a molding roll, a transfer roll, a transfer mold, a jig in contact with glass, and the like.
- the test apparatus 21 (FIG. 2) for evaluating the adhesiveness between the molten glass and the metal will be described.
- the test device 21 includes a glass rod holder 23 that supports the glass rod 22, a glass rod heating device 24 that heats the lower end of the glass rod 22, and a sample holder that supports the sample 20 at a predetermined angle below the glass rod heating device 24. It has 26 and a sample heating device 27 for heating the sample 20.
- the sample 20 is inclined at 70 degrees with respect to the horizontal plane, and its central portion is arranged 100 mm below the center point A of the frame 28.
- the sample heating device 27 is a metal plate provided with a heater 30 and a thermocouple 31 connected to the temperature controller 32.
- the glass rod heating device 24 has a quadrangular frame-shaped frame 28 and four burners 29 supported by the frame 28. Each burner 29 is supported by the frame 28 so that the injection holes face the inside of the frame 28 and the respective injection axes intersect at the center point A of the frame 28. Each burner 29 is adjusted so that the tips of the flames ejected from the burners 29 intersect at the center point A of the frame 28.
- the composition of the glass rod 22 is as follows: SiO 2 is 69% by mass, Al 2 O 3 is 1.7% by mass, Fe 2 O 3 is 0.06% by mass, Na 2 O is 8.5% by mass, and K 2 O is K 2 O. 4.9 wt%, MgO 2.2 wt%, CaO 4.0 wt%, SrO 6.0 wt%, BaO 3.2 wt%, Sb 2 O 3 is 0.3 wt%, P 2 O 5 is 0.2% by mass, TiO 2 is 0.03% by mass, Cl is 0.03% by mass, SO 3 is 0.03% by mass, and ZrO 2 is 0.1% by mass.
- the diameter of the glass rod is 4 mm.
- the lower end of the glass rod 22 is the center point of the frame 28. It was placed in A and heated by a flame ejected from each burner 29. The lower end of the heated glass rod becomes spherical and naturally falls and collides with the sample 20.
- the temperature of the glass block at the moment of collision is measured by thermography (Plex logger PL3 manufactured by Shinano Kenshi).
- Example 1 As an alloy raw material, with Ni as a residue component, Si with a particle size of 105 ⁇ m or less, Ni 2 P with a particle size of 150 ⁇ m or less, Cr with a particle size of 63 ⁇ m or less, Ni with a particle size of 2 to 3 ⁇ m, and Mo with a particle size of about 1.5 ⁇ m or less. Powder (both from High Purity Chemical Laboratory Co., Ltd.) and WC-12% Co (Utec Japan Co., Ltd.) with a particle size of 15-45 ⁇ m as hard particles are mixed at the ratios shown in Table 1 and subjected to pulse energization sintering method.
- a plate having a width of 3 cm, a depth of 4 cm, and a thickness of 3 mm and a surface roughness (arithmetic average roughness Ra) of about 1 ⁇ m or less was produced by additional machining. This plate was used as a sample 20 and a molten glass adhesiveness evaluation test was conducted.
- Example 2 A sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that 0.1% by mass of B having a particle size of 45 ⁇ m or less was further mixed as an alloy raw material.
- Example 3 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 2 except that B to be mixed was 0.5% by mass.
- Example 4 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 2 except that B to be mixed was 1.1% by mass and Si was 2.5% by mass.
- Example 5 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that 1.0% by mass of Si to be mixed was mixed.
- Example 6 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that 2.5% by mass of Si to be mixed was mixed.
- Example 7 A sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that Cr was not contained as an alloy raw material.
- Example 8 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that 20% by mass of Cr to be mixed was mixed.
- Example 9 Samples were prepared and evaluated in the same manner as in Example 4 except that Mo was not contained as an alloy raw material.
- Example 10 A sample was prepared and evaluated in the same manner as in Example 9 except that 0.4% by mass of V (vanadium) having a particle size of 150 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed as an alloy raw material.
- V vanadium
- Example 11 Examples except that WC-12% Co is not contained as an alloy raw material and WC having a particle size of about 5 ⁇ m and Co having a particle size of about 5 ⁇ m (both are high-purity chemical laboratories) are mixed at the ratio shown in Table 1. A sample was prepared and an evaluation test was conducted in the same manner as in 1.
- Example 12 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 11 except that Co was not contained.
- Example 13 After mixing the materials as the alloy raw material in the same ratio as in Example 1 and producing a metal plate by casting, the width is 3 cm, the depth is 4 cm, the thickness is 3 mm, and the surface roughness (arithmetic mean roughness Ra) is about 1 ⁇ m or less.
- the plate was prepared and evaluated.
- Example 14 As an alloy raw material, a sample was prepared in the same manner as in Example 12 except that 15.7% by mass of CrC (chromium carbide) (High Purity Chemical Laboratory Co., Ltd.) containing no WC fine particles and having a particle size of 45 ⁇ m or less was mixed. An evaluation test was conducted.
- CrC chromium carbide
- Example 15 As an alloy raw material, a sample was prepared in the same manner as in Example 12 except that 15.7% by mass of VC (vanadium carbide) (High Purity Chemical Laboratory Co., Ltd.) containing no WC fine particles and having an average particle size of 10 ⁇ m or less was mixed. And an evaluation test was conducted.
- VC vanadium carbide
- Example 16 Same as in Example 12 except that 15.7% by mass of ZrC (zirconium carbide) (High Purity Chemical Laboratory Co., Ltd.) containing no WC-12% Co and having an average particle size of 10 ⁇ m or less is mixed as an alloy raw material. Samples were prepared and evaluated.
- ZrC zirconium carbide
- Example 17 As an alloy raw material, a sample was prepared in the same manner as in Example 12 except that 5% by mass of SiC (silicon carbide) (High Purity Chemical Laboratory Co., Ltd.) containing no WC-12% Co and having an average particle size of 10 ⁇ m or less was mixed. Fabrication and evaluation tests were performed.
- SiC silicon carbide
- Example 18 As an alloy raw material, a sample was prepared in the same manner as in Example 4 except that WC-12% Co was not contained and 15.7% by mass of WC-10% Ni (Eutectic Japan Ltd.) having a particle size of 45 ⁇ m or less was mixed. An evaluation test was conducted.
- Example 19 As an alloy raw material, a sample was prepared in the same manner as in Example 4 except that WC-12% Co was not contained and 15.7% by mass of WC-10% Co4% Cr (Utectic Japan Ltd.) having a particle size of 45 ⁇ m or less was mixed. Fabrication and evaluation tests were performed.
- Example 20 As an alloy raw material, a sample was prepared in the same manner as in Example 4 except that WC-12% Co was not contained and 15.7% by mass of WC-20% Cr7% Ni (Eutectic Japan Ltd.) having a particle size of 45 ⁇ m or less was mixed. Preparation and evaluation tests were performed.
- Example 21 As an alloy raw material, a sample was prepared in the same manner as in Example 1 except that WC-12% Co was not contained and 6.7% by mass of CrC-20% Ni5% Cr (Utectic Japan Ltd.) having a particle size of 45 ⁇ m or less was mixed. Preparation and evaluation tests were performed.
- Example 22 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 21 except that CrC-20% Ni5% Cr to be mixed was adjusted to 15.7% by mass.
- Example 23 Samples were prepared and evaluated in the same manner as in Example 4 except that 15.7% by mass of CrC-20% Ni5% Cr having a particle size of 45 ⁇ m or less was mixed as an alloy raw material without containing WC-12% Co. It was.
- Example 24 Samples were prepared and evaluated in the same manner as in Example 4 except that 5% by mass of Ti (titanium) (High Purity Chemical Laboratory Co., Ltd.) containing no Cr and Mo and having a particle size of 45 ⁇ m or less was mixed as an alloy raw material. Was done.
- Example 25 Samples were prepared and evaluated in the same manner as in Example 4 except that 10% by mass of Zr (zirconium) (High Purity Chemical Laboratory Co., Ltd.) containing no Cr and Mo and having a particle size of 45 ⁇ m or less was mixed as an alloy raw material. Was done.
- Example 26 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 7 except that Mo to be mixed was 5% by mass.
- Example 27 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 7 except that Mo to be mixed was 10% by mass.
- Example 28 Samples were prepared and evaluated in the same manner as in Example 4 except that 10% by mass of Ta (tantalum) (High Purity Chemical Laboratory Co., Ltd.) containing no Cr and Mo and having a particle size of 45 ⁇ m or less was mixed as an alloy raw material. Was done.
- Ta tantalum
- Mo High Purity Chemical Laboratory Co., Ltd.
- Example 29 As an alloy raw material, a sample was prepared and an evaluation test was conducted in the same manner as in Example 1 except that V was mixed in an amount of 5% by mass.
- Example 30 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 10 except that the V to be mixed was 5% by mass.
- Example 31 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that 3% by mass of V and 10% by mass of Zr were mixed.
- Example 32 Samples were prepared and evaluated in the same manner as in Example 4 except that 10% by mass of W (tungsten) (High Purity Chemical Laboratory Co., Ltd.) containing no Cr and Mo and having an average particle size of 10 ⁇ m or less was mixed as an alloy raw material. The test was conducted.
- W tungsten
- Mo High Purity Chemical Laboratory Co., Ltd.
- Example 33 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that the WC-12% Co to be mixed was 5% by mass.
- Example 34 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that the WC-12% Co to be mixed was 20% by mass.
- Example 35 Samples were prepared and evaluated in the same manner as in Example 1 except that P was not contained as an alloy raw material.
- Example 36 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that P to be mixed was 3% by mass.
- Example 37 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 1 except that P to be mixed was 5% by mass.
- Example 38 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that Sb (antimony) having a particle size of 150 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed in an amount of 10% by mass.
- Example 39 As an alloy raw material, a sample was prepared and evaluated in the same manner as in Example 4 except that 5% by mass of Bi (bismuth) (High Purity Chemical Laboratory Co., Ltd.) containing no P and having a particle size of 150 ⁇ m or less was mixed. It was.
- Bi bismuth
- Example 40 A sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that cerium oxide was mixed in an amount of 10% by mass as an alloy raw material.
- Example 41 A sample was prepared and evaluated in the same manner as in Example 4 except that Y (yttrium) having a particle size of 150 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed as an alloy raw material in an amount of 1.11% by mass.
- Example 42 A sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that Y was mixed in an amount of 10% by mass as an alloy raw material.
- Example 43 As an alloy raw material, a sample was prepared and evaluated in the same manner as in Example 4 except that Mn (manganese) having an average particle size of 50 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed in an amount of 5% by mass.
- Mn manganese
- Example 44 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that Re (rhenium) having a particle size of 45 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed in an amount of 10% by mass.
- Example 45 As alloy materials, as a residual component of Ni, Si, Ni 2 P, Cr, Ni, and Mo and Fe (iron) powder (both Kojundo Chemical Laboratory Co., Ltd.), particle size 15-45 ⁇ m as hard particles WC Samples were prepared and evaluated in the same manner as in Example 13 except that -12% Co (Eutectic Japan Ltd.) was mixed at the ratio shown in Table 11.
- Example 46 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that Cu (copper) having an average particle size of 50 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed in an amount of 5% by mass.
- Example 47 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 4 except that 1.34% by mass of Ag (silver) having an average particle size of 50 ⁇ m or less (High Purity Chemical Laboratory Co., Ltd.) was mixed.
- Example 48 As an alloy raw material, a metal powder having a composition by ICP emission spectroscopy and a particle size (median diameter) by a laser diffraction / scattering method shown in Table 16 was prepared by a gas atomization method. After mixing the metal powder and WC-12% Co, the mixed powder is sprayed onto the surface of gray cast iron by a high-speed flame spraying method (HVOF (High Velocity Oxygen Fuel) method) to form a Ni-based alloy film having a thickness of about 0.8 mm. It was formed and used as a test piece. Table 14 shows the composition of the thermal spray coating when measured with a fluorescent X-ray analyzer.
- HVOF High Velocity Oxygen Fuel
- the test piece was additionally machined to prepare a plate having a width of 3 cm, a depth of 4 cm, and a thickness of 3 mm, and having a surface roughness (arithmetic mean roughness Ra) of about 1 ⁇ m or less.
- a molten glass adhesiveness evaluation test was conducted using the alloy film as an evaluation surface.
- Example 1 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Example 2 except that B to be mixed was adjusted to 5.0% by mass.
- Comparative Example 2 Samples were prepared and evaluated in the same manner as in Comparative Example 1 except that Si was not contained as an alloy raw material.
- Comparative Example 3 Samples were prepared and evaluated in the same manner as in Comparative Example 2 except that B and P were not contained as alloy raw materials.
- Comparative Example 4 A sample was prepared and an evaluation test was carried out in the same manner as in Comparative Example 2 except that P was not contained as an alloy raw material.
- Comparative Example 5 As an alloy raw material, a sample was prepared and an evaluation test was carried out in the same manner as in Comparative Example 2 except that P to be mixed was 3% by mass.
- FIG. 5 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 1 to 4 and Comparative Examples 1 and 2.
- the lower the adhesion rate the higher the slipperiness to the molten glass block.
- the adhesion rate was less than 10% as ⁇ (maru), and when the sample surface temperature was 10% or more, as x (x).
- the adhesive rate decreases as the B content decreases.
- Example 4 having a B content of 1.1% by mass satisfies the criterion, but Comparative Examples 1 and 2 having a B content of 5.0% by mass do not meet the criterion. That is, it can be seen that the threshold value of B that satisfies the criterion is in the range of more than 1.1% by mass and less than 5.0% by mass.
- the smaller the B content in the Ni-based self-soluble alloy the more preferable, for example, it is more than 0% by mass and less than 1.0% by mass.
- the slipperiness of the Ni-based self-soluble alloy with respect to the glass gob can be improved. Further, FIG.
- FIG. 23 shows the results of comparative examples 3 to 5, that is, the adhesiveness evaluation test for the molten glass block of the Ni-based self-soluble alloy containing no Si. From FIGS. 1 and 23, it can be seen that when Si is not contained, the slipperiness to the molten glass gob is poor regardless of the contents of B and P.
- the slipperiness to the molten glass gob can be improved.
- the alloy enables a fusing treatment by containing at least one flux component of B and Si.
- FIG. 7 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 4 and 7 to 10. From FIG. 7, it can be seen that the adhesion rate decreases as the Cr content increases, but even in Example 7 in which Cr is not contained, the determination criteria are satisfied.
- FIG. 10 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 14 to 16. From FIG. 10, if the carbide as the hard particle is a carbide of the elements of Group 4, 5 and 6 of the periodic table, the determination criteria are generally satisfied. Further, FIG. 11 shows the result of the adhesiveness evaluation test for the molten glass ingot of Example 17. From FIG. 11, even if the carbide as the hard particles is silicon carbide, the determination criteria are satisfied.
- FIG. 12 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 18 to 20. From FIG. 12, the judgment criteria are generally satisfied even if the binder metal of WC cermet and the content of Co are other than 12% Co. Further, FIG. 13 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 21 to 23. From FIG. 13, even if the carbide in the cermet as hard particles is CrC, the criterion is satisfied.
- FIG. 14 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 24 to 32. From FIG. 14, when the elements of Group 4, 5 and 6 of the periodic table are contained in the alloy, the judgment criteria are satisfied in various combinations and contents.
- FIG. 15 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 33 and 34. From FIG. 15, the content of WC-12% Co satisfies the criterion in a wide range.
- FIG. 16 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 35 to 39. From Examples 35 to 37, the judgment criteria are satisfied regardless of the content of P, which is one of the elements of Group 15 of the periodic table. Further, from Example 38, the determination criteria are satisfied even if two or more kinds of Group 15 elements are contained. Further, from Example 39, the selected Group 15 element does not necessarily have to be P, but satisfies the criterion.
- FIG. 17 shows the result of the adhesiveness evaluation test for the molten glass ingot of Example 40. From FIG. 17, the criterion is satisfied even if the type of hard particles is not metal carbide.
- FIG. 18 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 41 to 42. From FIG. 18, even if a Group 3 element is contained, the criterion is satisfied.
- FIG. 19 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 43 and 44. From FIG. 19, even if a Group 7 element is contained, the criterion is satisfied.
- FIG. 20 shows the result of the adhesiveness evaluation test for the molten glass block of Example 45. From FIG. 20, even if the Group 8 element is contained, the criterion is satisfied.
- FIG. 21 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 46 and 47. From FIG. 21, the judgment criteria are satisfied even if the Group 11 element is contained.
- FIG. 8 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 1, 11 and 12. From FIG. 8, it can be seen that whether cermet particles or finely divided carbides are used as a method for dispersing the hard particles in the Ni-based self-soluble alloy does not affect the sliding performance of the molten glass gob.
- FIG. 9 shows the results of the adhesiveness evaluation test for the molten glass ingots of Examples 1 and 13.
- the alloy may be produced directly from the raw material powder, or even if the alloy is produced by completely melting and solidifying the metal component once, the sliding performance of the molten glass gob It turns out that it does not affect. Therefore, for example, when the sprayed powder of the alloy is produced, a molten metal spraying method (atomizing method), a melt pulverization method, a sintering pulverization method, a granulation method, a granulation sintering method, a coating method, a mixing method, etc. are generally used. Various methods known to can be used.
- FIG. 22 shows the result of the adhesiveness evaluation test for the molten glass ingot of Example 48. From FIG. 22, it can be seen that, as a method for producing a Ni-based self-soluble alloy, even if it is produced by forming a film on the surface of some kind of base material, the sliding performance of the molten glass gob is not affected. Therefore, for example, when the alloy is formed into a film, various generally known methods such as thermal spraying, plating, clad, laminated molding, and welding can be used.
- the Ni-based self-soluble alloy of the present invention has a plate-like alloy whose surface is heated to 480 ° C. and is inclined 70 degrees with respect to a horizontal plane, and 0.3 g of molten glass heated to 1000 ( ⁇ 20 ° C.) ° C.
- the molten glass has the property of sliding down without adhering to the alloy when dropped, and due to this property, when the alloy is applied to the actual glass molding process, the friction with the molten glass block is small and good. Shows moldability.
- Glass manufacturing members using the Ni-based self-soluble alloy of the present invention include metal members such as molds, plungers, and rollers, as well as shooters used in the bottle making process for transporting molten glass ingots. It can also be applied to a transport member.
Abstract
Description
溶融ガラスと金属との接着性を評価するための試験装置21(図2)について説明する。試験装置21はガラス棒22を支持するガラス棒ホルダ23と、ガラス棒22の下端を加熱するガラス棒加熱装置24と、ガラス棒加熱装置24の下方においてサンプル20を所定の角度で支持するサンプルホルダ26と、サンプル20を加熱するサンプル加熱装置27とを有する。
ガラス棒22の組成は、SiO2が69質量%、Al2O3が1.7質量%、Fe2O3が0.06質量%、Na2Oが8.5質量%、K2Oが4.9質量%、MgOが2.2質量%、CaOが4.0質量%、SrOが6.0質量%、BaOが3.2質量%、Sb2O3が0.3質量%、P2O5が0.2質量%、TiO2が0.03質量%、Clが0.03質量%、SO3が0.03質量%、ZrO2が0.1質量%である。ガラス棒の直径は4mmである。
サンプル20の表面温度を温度センサ(安立計器株式会社製静止表面用温度センサ A形シリーズ)で測定することにより所定の温度であることを確認した後、ガラス棒22の下端をフレーム28の中心点Aに配置し、各バーナ29から噴射される火炎によって加熱した。加熱されたガラス棒下端は球状となり、自然に落下してサンプル20と衝突する。衝突した瞬間のガラス塊温度をサーモグラフィ(シナノケンシ製プレクスロガーPL3)により測定する。
サンプル20と衝突したガラス塊はサンプル20に接着(付着)するか或は接着せずに下方に落下する。サンプル20と衝突した瞬間のガラス塊の温度が1000(±20)℃の範囲内であった時、サンプル20表面に接着して留まったものを「接着有り」、サンプル20表面に接着せず下方に落下したものを「接着なし」と判定した。この試験を、あるサンプル20表面温度において10回実施し、10回中の「接着有り」の割合を接着率(%)とした。なお、溶融ガラスの温度範囲が上述の範囲から外れた時は評価の対象としなかった。
合金原料として、Niを残渣成分として、粒径105μm以下のSi、粒径150μm以下のNi2P、粒径63μm以下のCr、粒径2~3μmのNi及び粒径約1.5μm以下のMo粉末(いずれも株式会社高純度化学研究所)と、硬質粒子として粒径15-45μmのWC-12%Co(ユテクジャパン株式会社)を表1に示す割合で混合し、パルス通電焼結法により金属板を作製した後、追加工により幅3cm奥行4cm厚さ3mmで、表面粗さ(算術平均粗さRa)が約1μm以下の板を作製した。この板をサンプル20として用い溶融ガラス接着性評価試験を行った。
合金原料として、さらに粒径45μm以下のBを0.1質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するBを0.5質量%にすること以外は実施例2と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するBを1.1質量%とし、Siを2.5質量%としたこと以外は実施例2と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するSiを1.0質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するSiを2.5質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、Crを含まないこと以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するCrを20質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Moを含まないこと以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、粒径150μm以下のV(バナジウム)(株式会社高純度化学研究所)を0.4質量%混合すること以外は実施例9と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径約5μmのWCと粒径約5μmのCo(いずれも株式会社高純度化学研究所)を表1の割合で混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、Co含まないこと以外は実施例11と同様にサンプルを作製及び評価試験を行った。
合金原料として実施例1と同じ割合で材料を混合し、鋳造により金属板を作製した後、追加工により幅3cm奥行4cm厚さ3mmで、表面粗さ(算術平均粗さRa)が約1μm以下の板を作製し、評価試験を行った。
合金原料として、WC微粒子を含まず、粒径45μm以下のCrC(炭化クロム)(株式会社高純度化学研究所)を15.7質量%混合すること以外は実施例12と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC微粒子を含まず、平均粒径10μm以下のVC(炭化バナジウム)(株式会社高純度化学研究所)を15.7質量%混合すること以外は実施例12と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、平均粒径10μm以下のZrC(炭化ジルコニウム)(株式会社高純度化学研究所)を15.7質量%混合すること以外は実施例12と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、平均粒径10μm以下のSiC(炭化ケイ素)(株式会社高純度化学研究所)を5質量%混合すること以外は実施例12と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径45μm以下のWC-10%Ni(ユテクジャパン株式会社)を15.7質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径45μm以下のWC-10%Co4%Cr(ユテクジャパン株式会社)を15.7質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径45μm以下のWC-20%Cr7%Ni(ユテクジャパン株式会社)を15.7質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径45μm以下のCrC-20%Ni5%Cr(ユテクジャパン株式会社)を6.7質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するCrC-20%Ni5%Crを15.7質量%にすること以外は実施例21と同様にサンプルを作製及び評価試験を行った。
合金原料として、WC-12%Coを含まず、粒径45μm以下のCrC-20%Ni5%Crを15.7質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Cr及びMoを含まず、粒径45μm以下のTi(チタン)(株式会社高純度化学研究所)を5質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Cr及びMoを含まず、粒径45μm以下のZr(ジルコニウム)(株式会社高純度化学研究所)を10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するMoを5質量%にすること以外は実施例7と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するMoを10質量%にすること以外は実施例7と同様にサンプルを作製及び評価試験を行った。
合金原料として、Cr及びMoを含まず、粒径45μm以下のTa(タンタル)(株式会社高純度化学研究所)を10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Vを5質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するVを5質量%にすること以外は実施例10と同様にサンプルを作製及び評価試験を行った。
合金原料として、Vを3質量%、Zrを10質量%混合すること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、Cr及びMoを含まず、平均粒径10μm以下のW(タングステン)(株式会社高純度化学研究所)を10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するWC-12%Coを5質量%にすること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するWC-12%Coを20質量%にすること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Pを含まないこと以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するPを3質量%にすること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するPを5質量%にすること以外は実施例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、粒径150μm以下のSb(アンチモン)(株式会社高純度化学研究所)を10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Pを含まず、粒径150μm以下のBi(ビスマス)(株式会社高純度化学研究所)を5質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、酸化セリウムを10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、粒径150μm以下のY(イットリウム)(株式会社高純度化学研究所)を1.11質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Yを10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、平均粒径50μm以下のMn(マンガン)(株式会社高純度化学研究所)を5質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、粒径45μm以下のRe(レニウム)(株式会社高純度化学研究所)を10質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、Niを残渣成分として、Si、Ni2P、Cr、Ni、Mo及びFe(鉄)粉末(いずれも株式会社高純度化学研究所)と、硬質粒子として粒径15-45μmのWC-12%Co(ユテクジャパン株式会社)を表11に示す割合で混合すること以外は実施例13と同様にサンプルを作製及び評価試験を行った。
合金原料として、平均粒径50μm以下のCu(銅)(株式会社高純度化学研究所)を5質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、平均粒径50μm以下のAg(銀)(株式会社高純度化学研究所)を1.34質量%混合すること以外は実施例4と同様にサンプルを作製及び評価試験を行った。
合金原料として、ガスアトマイズ法によりICP発光分光分析法による組成及びレーザ回折・散乱法による粒径(メジアン径)が表16に記載された組成及び粒径である金属粉末を作製した。該金属粉末とWC-12%Coを混合した後、該混合粉末を高速フレーム溶射法(HVOF(High Velocity Oxygen Fuel)法)によりねずみ鋳鉄表面に溶射し厚み約0.8mmのNi基合金皮膜を形成し試験片とした。溶射皮膜の組成を蛍光X線分析装置で測定したところ表14となっていた。該試験片を追加工により幅3cm奥行4cm厚さ3mmで、該合金皮膜の表面粗さ(算術平均粗さRa)が約1μm以下の板を作製した。この板を実施例48として用い該合金皮膜を評価面として溶融ガラス接着性評価試験を行った。
合金原料として、混合するBを5.0質量%にすること以外は実施例2と同様にサンプルを作製及び評価試験を行った。
合金原料として、Siを含まないこと以外は比較例1と同様にサンプルを作製及び評価試験を行った。
合金原料として、B及びPを含まないこと以外は比較例2と同様にサンプルを作製及び評価試験を行った。
合金原料として、Pを含まないこと以外は比較例2と同様にサンプルを作製及び評価試験を行った。
合金原料として、混合するPを3質量%にすること以外は比較例2と同様にサンプルを作製及び評価試験を行った。
図5は、実施例1~4と比較例1及び2の溶融ガラス塊に対する接着性評価試験の結果である。各サンプル表面温度において、接着率が低いほど溶融ガラス塊に対する滑り性が高いことを示している。評価の判定基準として、サンプル表面温度が480℃、500℃及び520℃のときの接着率が10%未満の時を○(マル)、10%以上の時を×(バツ)とした。図5からわかるように、Bの含有量が低下するほど接着率は低下することがわかる。Bの含有量が1.1質量%である実施例4は判定基準を満たすが、Bの含有量が5.0質量%である比較例1及び2は判定基準を満たさない。すなわち、判定基準を満たすBの閾値は、1.1質量%より大きく5.0質量%より小さい範囲にあることがわかる。Ni基自溶性合金におけるBの含有量は少ないほど好ましく、例えば0質量%より大きく1.0質量%未満であるとよい。Bの含有量を低減させることによって、Ni基自溶性合金のガラス塊に対する滑り性を向上させることができる。また、図6は実施例1、5及び6、すなわちNi基自溶性合金中にBを含まないときの溶融ガラス塊に対する接着性評価試験の結果である。図5と同様に、図6よりSiが1.0~5.0質量%の範囲においては溶融ガラス塊に対する滑り性が良好であることが分かる。
図7は、実施例4、7~10の溶融ガラス塊に対する接着性評価試験の結果である。図7から、Crの含有量が増加するほど接着率が低下することがわかるが、Crが含まれていない実施例7でも判定基準を満たす。
図10は、実施例14~16の溶融ガラス塊に対する接着性評価試験の結果である。図10から、硬質粒子としての炭化物が周期表第4,5,6族元素の炭化物であれば判定基準を概ね満たす。また、図11は、実施例17の溶融ガラス塊に対する接着性評価試験の結果である。図11から、硬質粒子としての炭化物が炭化ケイ素であっても判定基準を満たす。
図12は、実施例18~20の溶融ガラス塊に対する接着性評価試験の結果である。図12から、WCサーメットのバインダー金属及び含有量が12%のCo以外であっても判定基準を概ね満たす。また、図13は、実施例21~23の溶融ガラス塊に対する接着性評価試験の結果である。図13から、硬質粒子としてのサーメット中の炭化物がCrCであっても判定基準を満たす。
図14は、実施例24~32の溶融ガラス塊に対する接着性評価試験の結果である。図14から、周期表第4,5,6族元素を合金中に含有させる際、多様な組み合わせかつ含有量において判定基準を満たす。
図15は、実施例33及び34の溶融ガラス塊に対する接着性評価試験の結果である。図15から、WC-12%Coの含有量が広い範囲で判定基準を満たす。
図16は、実施例35~39の溶融ガラス塊に対する接着性評価試験の結果である。実施例35~37から、周期表第15族元素の一つであるPの含有量によらず判定基準を満たす。また、実施例38から、2種類以上の第15族元素を含んでも判定基準を満たす。さらに、実施例39から、選択される第15族元素は必ずしもPでなくても判定基準を満たす。
図17は、実施例40の溶融ガラス塊に対する接着性評価試験の結果である。図17から、硬質粒子の種類が金属炭化物でなくても判定基準を満たす。
図18は、実施例41~42の溶融ガラス塊に対する接着性評価試験の結果である。図18から、第3族元素が含有されていても判定基準を満たす。
図19は、実施例43及び44の溶融ガラス塊に対する接着性評価試験の結果である。図19から、第7族元素が含有されていても判定基準を満たす。
図20は、実施例45の溶融ガラス塊に対する接着性評価試験の結果である。図20から、第8族元素が含有されていても判定基準を満たす。
図21は、実施例46及び47の溶融ガラス塊に対する接着性評価試験の結果である。図21から、第11族元素が含有されていても判定基準を満たす。
図8は、実施例1、11及び12の溶融ガラス塊に対する接着性評価試験の結果である。図8から、Ni基自溶性合金中に硬質粒子を分散させる方法として、サーメット粒子を用いても、微粒子状の炭化物を用いても溶融ガラス塊の滑り性能には影響しないことが分かる。
図9は、実施例1及び13の溶融ガラス塊に対する接着性評価試験の結果である。図9から、Ni基自溶性合金の作製方法として、原料粉末から直接合金を作製しても良いし、一度金属成分を完全に溶解させて凝固させることで作製しても溶融ガラス塊の滑り性能には影響しないことが分かる。従って、例えば該合金の溶射粉末を作製する際は、溶湯噴霧法(アトマイズ法)、溶融粉砕法、焼結粉砕法、造粒法、造粒焼結法、被覆法、混合法など、一般的に知られている様々な方法を用いることができる。
15 :金属酸化皮膜
16 :溶融ガラス塊
20 :サンプル
21 :溶融ガラス接着性評価試験装置
22 :ガラス棒
23 :ガラス棒ホルダ
24 :ガラス棒加熱装置
26 :サンプルホルダ
27 :サンプル加熱装置
28 :バーナ支持フレーム
29 :バーナ
30 :ヒータ
31 :熱電対
32 :温度調節器
42 :金型
43 :溶融ガラス槽
44 :溶融ガラス搬送部材
Claims (33)
- 粘度がlogη=3~14.6のガラスを搬送又は成形するためのガラス製造用部材に用いるNi基自溶性合金であって、
0質量%以上1.5質量%以下のBと、硬質粒子と、Siとを含むNi基自溶性合金。 - 前記Bが0質量%以上1.0質量%未満である請求項1に記載のNi基自溶性合金。
- 前記Bが0質量%より大きく1.0質量%未満である請求項1に記載のNi基自溶性合金。
- 周期表第15族元素から選択された少なくとも1つの元素を含む請求項1~請求項3のいずれか1つの項に記載のNi基自溶性合金。
- 周期表第15族元素から選択された少なくとも1つの元素は、Pを含む請求項4に記載のNi基自溶性合金。
- 前記周期表第15族元素から選択された少なくとも1つの元素を0質量%以上15質量%以下含む請求項4又は請求項5に記載のNi基自溶性合金。
- 前記硬質粒子が炭化物、窒化物、酸化物及びサーメットの少なくとも1つを含む請求項1~請求項6のいずれか1つに記載のNi基自溶性合金。
- 前記炭化物が周期表第4、5及び6族元素のいずれか1つの炭化物を含む請求項7に記載のNi基自溶性合金。
- 前記炭化物が炭化ケイ素である請求項7に記載のNi基自溶性合金。
- 前記サーメットが周期表第4、5及び6族元素のいずれか1つの炭化物を含む請求項7に記載のNi基自溶性合金。
- 前記酸化物がランタノイドから選択された少なくとも1つの金属の酸化物を含む請求項7に記載のNi基自溶性合金。
- 前記ランタノイドから選択された少なくとも1つの金属の酸化物が酸化セリウムである請求項10に記載のNi基自溶性合金。
- 周期表第4、5及び6族元素から選択された少なくとも1つの金属を0質量%より大きく30質量%以下含む請求項1~請求項12のいずれか1つの項に記載のNi基自溶性合金。
- 周期表第4、5及び6族元素から選択された少なくとも1つの前記金属はCrを含む請求項13に記載のNi基自溶性合金。
- 前記Siが1質量%以上7.5質量%以下、前記硬質粒子が5質量%以上50質量%以下、前記金属が2.5質量%以上30質量%以下のCrである請求項13又は請求項14に記載のNi基自溶性合金。
- 第3族元素から選択された少なくとも1つの金属を含む請求項1~請求項15のいずれか1つの項に記載のNi基自溶性合金。
- 前記第3族元素から選択された少なくとも1つの前記金属を0質量%以上10質量%以下含む請求項16に記載のNi基自溶性合金。
- 前記第3族元素から選択された少なくとも1つの前記金属がYである請求項17に記載のNi基自溶性合金。
- 第7族元素から選択された少なくとも1つの金属を含む請求項1~請求項15のいずれか1つの項に記載のNi基自溶性合金。
- 前記第7族元素から選択された少なくとも1つの前記金属を0質量%以上10質量%以下含む請求項19に記載のNi基自溶性合金。
- 前記第7族元素から選択された少なくとも1つの前記金属がMn又はReである請求項20に記載のNi基自溶性合金。
- 第8族元素から選択された少なくとも1つの金属を含む請求項1~請求項15のいずれか1つの項に記載のNi基自溶性合金。
- 前記第8族元素から選択された少なくとも1つの前記金属を0質量%以上30質量%以下含む請求項22に記載のNi基自溶性合金。
- 前記第8族元素から選択された少なくとも1つの前記金属がFeである請求項23に記載のNi基自溶性合金。
- 第11族元素から選択された少なくとも1つの金属を含む請求項1~請求項15のいずれか1つの項に記載のNi基自溶性合金。
- 前記第11族元素から選択された少なくとも1つの前記金属を0質量%以上10質量%以下含む請求項25に記載のNi基自溶性合金。
- 前記第11族元素から選択された少なくとも1つの前記金属がCu又はAgである請求項26に記載のNi基自溶性合金。
- 表面の温度が480℃に加熱され、水平面に対して70度傾斜した板状の前記Ni基自溶性合金に、1000℃に加熱された溶融ガラス0.3gを滴下したときに、溶融ガラスが前記Ni基自溶性合金に接着せずに滑り落ちる請求項1~請求項27のいずれか1つの項に記載のNi基自溶性合金。
- 前記ガラス製造用部材は、400℃以上1400℃以下のガラスを搬送又は成形するための部材である請求項1~請求項28のいずれか1つの項に記載のNi基自溶性合金。
- 請求項1~請求項29のいずれか1つの項に記載の前記Ni基自溶性合金を用いて、ガラスの成形加工において溶融ガラスと接触する部位を形成したガラス製造用部材。
- 前記溶融ガラスと接触する前記部位に前記Ni基自溶性合金が溶射されている請求項30に記載のガラス製造用部材。
- 請求項30又は請求項31に記載のガラス製造用部材によって形成したガラスびん成形用の金型。
- 請求項30又は請求項31に記載のガラス製造用部材によって形成したガラス塊搬送用部材。
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- 2020-05-19 KR KR1020217041981A patent/KR102650768B1/ko active IP Right Grant
- 2020-05-19 US US17/613,412 patent/US11643708B2/en active Active
- 2020-05-19 EP EP20808632.2A patent/EP3974552A4/en active Pending
- 2020-05-19 WO PCT/JP2020/019745 patent/WO2020235547A1/ja unknown
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US11643708B2 (en) | 2023-05-09 |
CN113840932B (zh) | 2023-06-16 |
CN113840932A (zh) | 2021-12-24 |
KR102650768B1 (ko) | 2024-03-25 |
EP3974552A4 (en) | 2023-08-09 |
JPWO2020235547A1 (ja) | 2020-11-26 |
US20220251684A1 (en) | 2022-08-11 |
KR20220012902A (ko) | 2022-02-04 |
JP7142159B2 (ja) | 2022-09-26 |
TWI786407B (zh) | 2022-12-11 |
TW202104610A (zh) | 2021-02-01 |
EP3974552A1 (en) | 2022-03-30 |
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