EP3249066B1 - Zierelement aus cermet und uhr, tragbares endgerät und daraus erhaltenes zubehör - Google Patents

Zierelement aus cermet und uhr, tragbares endgerät und daraus erhaltenes zubehör Download PDF

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Publication number
EP3249066B1
EP3249066B1 EP16755638.0A EP16755638A EP3249066B1 EP 3249066 B1 EP3249066 B1 EP 3249066B1 EP 16755638 A EP16755638 A EP 16755638A EP 3249066 B1 EP3249066 B1 EP 3249066B1
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Prior art keywords
mass
cermet
nickel
decorative member
present
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EP16755638.0A
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English (en)
French (fr)
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EP3249066A4 (de
EP3249066A1 (de
Inventor
Yoshito TANI
Shunji Mikaki
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Kyocera Corp
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Kyocera Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/02—Link constructions
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • B22F5/106—Tube or ring forms
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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

Definitions

  • the present invention relates to a cermet decorative member, and a watch, a mobile terminal, and an accessory obtained using the same.
  • the present inventors have proposed various cermet decorative members exhibiting a gold color.
  • Patent Document 1 proposes a cermet decorative member which is a ceramic for a decorative part including a titanium nitride sintered compact including titanium nitride as a primary component, wherein the member contains nickel, niobium, chromium, and carbon, and the carbon content is not less than 0.5 mass% and not greater than 0.9 mass%.
  • Patent Document 2 proposes a cermet decorative member, which includes a ceramic for a decorative part including a titanium nitride sintered compact, wherein the ceramic contains nickel, niobium, chromium, and carbon, and the carbon content is not less than 1 mass% and not greater than 2 mass%.
  • EP 2298948 A1 proposes ceramics for a decorative component composed of a titanium nitride-based sintered body, wherein the titanium nitride-based sintered body contains nickel, niobium, chromium, and carbon having a content of not less than 1% by mass nor more than 2% by mass.
  • EP 2568055 A1 proposes a lightweight material for decorative parts having a silver metallic color tone including a sintered body having a main hard phase composed of a solid solution formed of titanium carbonitride and titanium carbide, a main binder phase composed of nickel, a first additive material composed of at least one selected from the group consisting of molybdenum carbide, niobium carbide, tungsten carbide, and tantalum carbide, a second additive material composed of at least one of chromium and chromium carbide, and the balance being incidental impurities.
  • JP 2011130894 A proposes a molded piece for an ornamental part comprising a titanium nitride material including nickel, niobium, chromium, and carbon.
  • the present invention is directed at a cermet decorative member according to independent claim 1. Furthermore, the present invention is directed at a watch, a mobile terminal, and an accessory according to independent claims 2 to 4.
  • the cermet decorative member includes a cermet containing a crystal phase including titanium carbonitride and a bonding phase including metal.
  • the bonding phase contains nickel as the primary component and at least niobium and chromium, wherein the lattice constant of the nickel is not less than 3.54 ⁇ .
  • the primary component in the bonding phase is a component exceeding 50 mass% per 100 mass% of components constituting the bonding phase.
  • the cermet decorative member of the present embodiment satisfying the configuration above exhibits a color tone in the gold family with little color variation.
  • the lattice constant of nickel single crystal is 3.5238 ⁇
  • the lattice constant of nickel in the cermet decorative member of the present embodiment is not less than 3.54 ⁇ . It is surmised that the cermet decorative member of the present embodiment exhibits a color tone in the gold family with little color variation because at least one of niobium and chromium forms a solid solution with nickel, which is the primary component of the bonding phase and has a high ionization tendency, and this reduces the ionization tendency of nickel. In particular, it is surmised that niobium forming a solid solution has a large effect.
  • the lattice constant of nickel in the cermet decorative member of the present embodiment can be measured using an X-ray diffractometer (XRD; e.g., D8 ADVANCE, manufactured by Bruker AXS GmbH).
  • XRD X-ray diffractometer
  • nickel is from 7.0 to 11.0 mass%, niobium is from 1.5 to 6.0 mass%, chromium is from 1.0 to 5.0 mass%, and the remainder is titanium carbonitride per 100 mass% of all components that constitute the cermet. More preferably, nickel is from 8.0 to 10.0 mass%, niobium is from 2.5 to 5.0 mass%, and chromium is from 2.0 to 4.0 mass%. Note that the presence or absence of titanium carbonitride in the cermet decorative member of the present embodiment may be verified by XRD measurement and identification. Furthermore, the presence of nickel, niobium, and chromium in a portion other than the crystal phase can be verified by observation by a scanning electron microscope (SEM), and by using an EDS equipped with the SEM.
  • SEM scanning electron microscope
  • the contents of nickel, niobium, and chromium may be determined by measurement using an inductively coupled plasma emission spectrophotometer (ICP) or a fluorescent X-ray analyzer (XRF).
  • the titanium carbonitride content may be determined by subtracting the sum of nickel, niobium, and chromium contents from 100 mass%.
  • the titanium carbonitride content may also be determined by measuring Ti by ICP or XRF, and adding up the results of measuring carbon using a carbon analyzer and nitrogen measured using a nitrogen analyzer.
  • nickel From the nickel content and the sum of nickel, niobium, and chromium contents, it can be verified whether or not nickel is the primary component.
  • CM-5 spectrophotometric colorimeter
  • L* also simply called “L*” hereinafter
  • a* psychometric chroma coordinate a*
  • b* psychometric chroma coordinate b*
  • SCI spectrum component included
  • a CIE standard light source D65 may be used as a light source
  • the illumination receiving mode may be di: 8° ⁇ de: 8° (diffuse illumination ⁇ 8° direction reception)
  • the measurement diameter may be 3 mm.
  • ⁇ E [( ⁇ L*) 2 + ( ⁇ a*) 2 + ( ⁇ b*) 2 ] 1/2 using the obtained values of L*, a*, and b*.
  • L* is an index of brightness expressing the lightness and darkness of a color tone.
  • the larger value of L* indicates a bright color tone, while the smaller value of L* indicates the darker color tone.
  • a* is an index expressing the position between red and green of a color tone. If a* is a large positive value, the color tone is in the red family, and if it is a large negative value, the color tone is in the green family.
  • b* is an index expressing the position between yellow and blue of a color tone. If b* is a large positive value, the color tone is in the yellow family, and if it is a large negative value, the color tone is in the blue family.
  • the lattice constant of the titanium carbonitride crystal phase has a lattice constant of 4.27 ⁇ or more and 4.30 ⁇ or less
  • the above L* is not less than 64 and not greater than 68
  • a* is not less than 1 and not greater than 4
  • b* is not less than 1 and not greater than 5.
  • the cermet decorative member of the present embodiment when the cermet contains at least one of molybdenum, tungsten, and cobalt, they act as sintering aids and the firing temperature can be reduced. As a result, a decrease in shape workability due to abnormal grain growth of titanium carbonitride can be suppressed.
  • the cermet contains at least one of molybdenum, tungsten, and cobalt.
  • the contents are not less than 0.5 mass% and not greater than 2.0 mass% of molybdenum, not less than 0.05 mass% and not greater than 0.4 mass% of tungsten, and not less than 0.02 mass% and not greater than 0.2 mass% of cobalt, per 100 mass% of all components constituting the cermet.
  • the sum of molybdenum, tungsten, and cobalt contents is not greater than 2 mass%.
  • the cermet contains all of molybdenum, tungsten, and cobalt.
  • the contents of molybdenum, tungsten, and cobalt per 100 mass% of all components constituting the cermet may be measured using ICP or XRF.
  • the oxygen content when the oxygen content is less than 1.0 mass% per 100 mass% of all components constituting the cermet, there is little oxidation of the bonding phase, and color variation can therefore be further reduced. Furthermore, when the oxygen content is less than 1.0 mass%, there is little oxidation of the bonding phase, i.e. nickel, niobium, chromium, and the like are present as metals. As a result, it can play a sufficient role as a bonding phase.
  • the oxygen content may be determined by measurement using an oxygen analyzer (e.g., TCH-600, manufactured by LECO Corporation).
  • the shape processing time for making the desired shape can be reduced while mechanical characteristics as a decorative member are maintained.
  • Free carbon content may be determined by measurement using a carbon analyzer (e.g., RC-612, manufactured by LECO Corporation).
  • a Compound including nickel and chromium may also be present in the cermet decorative member of the present embodiment.
  • Nickel and chromium are magnetic, whereas a compound including nickel and chromium is non-magnetic. Thus, when the compound including nickel and chromium is present, it tends not to have a magnetic effect when the cermet decorative member is used in a watch, mobile terminal, or the like.
  • a compound including nickel and chromium indicates a compound represented as CrNi.
  • the JCPDS number of CrNi is 01-071-7594.
  • the cermet decorative member of the present embodiment has three-point bending strength of not less than 1000 MPa, and has sufficient mechanical characteristics for practical use. Three-point bending strength may be measured according to JIS R 1601-2008.
  • FIGS. 1A and 1B illustrate a watch case as an example of a cermet decorative member of the present embodiment.
  • FIG. 1A is a perspective view seen from the front side
  • FIG. 1B is a perspective view seen from the rear side.
  • FIG. 2 is a schematic view illustrating an example of a configuration of a watchband as an example of a cermet decorative member of the present embodiment.
  • the watch case 10 illustrated in FIGS. 1A and 1B includes a recessed portion 11 housing a movement (drive mechanism) and the like (not illustrated), and lug portions 12 which affix a watchband (not illustrated) for wearing the watch on the wrist.
  • the recessed portion 11 is made from a thin bottom portion 13 and a thick torso portion 14.
  • the band pieces constituting the watchband 50 illustrated in FIG. 2 are configured from center pieces 20 each having through-holes 21 into which pins 40 are inserted, and outer pieces 30 arranged so as to sandwich the center pieces 20, each of the outer pieces 30 having pin holes 31 through which the pins 40 are inserted.
  • the watchband 50 is configured by the center pieces 20 and the outer pieces 30 being sequentially connected by means of the pins 40 being inserted in the through-holes 21 of the center pieces 20 and both ends of the inserted pins 40 being inserted into the pin holes 31 of the outer pieces 30.
  • the watch case 10 and the band pieces constituting the watchband 50 including the cermet decorative member of the present embodiment can exhibit a color tone in the gold family with little color variation, and as a result, provide a consumer with a luxury feel and an esthetically pleasing look.
  • a watch including the cermet decorative member of the present embodiment in the watch case 10, the band pieces constituting the watchband 50, and the like can also provide a consumer with a luxury feel and an esthetically pleasing look.
  • the cermet decorative member of the present embodiment may also be used in the hands and face of a watch.
  • the cermet decorative member of the present embodiment may also be suitably used in cases, various operation keys, and the like of mobile terminals. As such, it provides a consumer who owns the mobile terminal including the cermet decorative member of the present embodiment with a luxury feel and esthetically pleasing look.
  • a mobile terminal is a portable information terminal that includes a mobile telephone, or a portable car navigation device, audio player, or the like.
  • the cermet decorative member of the present embodiment may be suitably used in a ring, an earring, a necklace and the like, and provides a consumer who owns such an accessory with a luxury feel and esthetically pleasing look.
  • the cermet decorative member of the present embodiment may be suitably used in parts that require decorative value, such as amenity goods, vehicle emblems, and the like.
  • titanium nitride powder having an average particle size of from 10 to 30 ⁇ m titanium carbide powder having an average particle size of from 0.5 to 3.0 ⁇ m, nickel powder having an average particle size of from 15 to 25 ⁇ m, niobium powder having an average particle size of from 10 to 20 ⁇ m, and chromium powder having an average particle size of from 30 to 50 ⁇ m are weighed out.
  • titanium nitride powder and titanium carbide powder are used as starting raw materials.
  • the weights of titanium nitride powder and titanium carbide powder are preferably chosen to be in the ratio of from 6.5:3.5 to 3:7, and more preferably from 6:4 to 4:6.
  • the nickel powder, niobium powder, chromium powder, and water or methanol as a solvent are loaded into a mill, where they are mixed and ground (primary mixing and grinding). Grinding only the metal powders for not less than 10 hours leads to the presence of the niobium powder and chromium powder on the periphery of the nickel powder, and at least one of niobium and chromium can form a solid solution in nickel.
  • the duration of primary mixing and grinding is greater than 30 hours, the effect of promoting solid solution formation reaches its plateau, and therefore the duration of primary mixing and grinding for the purpose of promoting solid solution formation is preferably not greater than 30 hours.
  • the cermet contains at least one of molybdenum, tungsten, and cobalt, molybdenum powder, tungsten powder, and cobalt powder may be prepared and added during primary mixing and grinding. Furthermore, for a compound including nickel and chromium to be present in the cermet, the duration of primary mixing and grinding may be not less than 30 hours.
  • the titanium nitride powder and titanium carbide powder are introduced into the mill, and secondary mixing and grinding are performed.
  • a prescribed amount of a binder is then added to obtain a slurry.
  • the obtained slurry is then spray-dried to form granules, and these granules are molded into a desired shape, such as a round plate, flat plate, annular body, or the like, using a desired molding method, such as dry pressing, cold isostatic pressing, extrusion molding, or the like. If the desired shape is complex, injection molding may also be used as the molding method.
  • the powder compact is placed in a pressure degreasing furnace and degreased while maintaining a temperature at from 310 to 390°C and a pressure at from 30 to 60 kPa in an inert gas atmosphere.
  • the degreased powder compact may then be fired at from 1200 to 1500°C in vacuum of not greater than 1.33 Pa to produce a sintered compact.
  • the oxygen content of less than 1.0 mass% per 100 mass% of all components constituting the cermet, it may be held at from 400 to 600°C for not less than 50 minutes when increasing the temperature of firing, and then fired at from 1200 to 1500°C.
  • the degreasing conditions may be adjusted. For example, when the temperature is 350°C and the pressure is 45 kPa, the hold time may be from 10 to 20 minutes.
  • lap processing is performed using, for example, a tin lapping plate while supplying diamond abrasive grains having an average particle size of not greater than 1 ⁇ m, and then barrel polishing is performed.
  • the compact may be tumbled in a rotary barrel polisher for 24 hours using green carborundum (GC) as a medium.
  • GC green carborundum
  • the cermet decorative member of the present embodiment obtained in the above manner contains a crystal phase including titanium carbonitride and a bonding phase including nickel, niobium, and chromium.
  • the lattice constant of the nickel is not less than 3.54 ⁇ , and it can exhibit a gold color tone with little color variation.
  • the watch, mobile terminal, and accessory obtained using the cermet decorative member of the present embodiment has sufficient mechanical strength for practical use, and can also provide a consumer with a luxury feel and an esthetically pleasing look.
  • titanium nitride powder having an average particle size of 20 ⁇ m, titanium carbide powder having an average particle size of 1.0 ⁇ m, nickel powder having an average particle size of 20 ⁇ m, niobium powder having an average particle size of 15 ⁇ m, and chromium powder having an average particle size of 40 ⁇ m were weighed out.
  • a nickel content is 10 mass%
  • a niobium content is 5.0 mass%
  • a chromium content is 3 mass% in the cermet.
  • the ratio of titanium nitride powder to titanium carbide powder was 6:4.
  • the nickel powder, niobium powder, chromium powder, and water or methanol as a solvent were loaded into a mill, where primary mixing and grinding were performed for the time shown in Table 1.
  • the obtained slurry was spray-dried to form granules, and using these granules, a powder compact was obtained by dry compression molding.
  • the powder compact was placed in a pressure degreasing furnace and degreased while maintaining a temperature at 350°C and a pressure at 45 kPa in an inert gas atmosphere, and the degreased powder compact was then fired at a temperature of 1500°C in vacuum of not greater than 1.33 Pa to obtain a sintered compact.
  • measurement conditions SCI (specular component included) conditions were used, a CIE standard light source D65 was used as a light source, the illumination receiving mode was di: 8° ⁇ de: 8° (diffuse illumination ⁇ 8° direction reception), and the measurement diameter was 3 mm.
  • Sample Nos. 3 to 6 have a smaller value of ⁇ E than Sample Nos. 1 and 2, and it was found that in a cermet containing a crystal phase including titanium carbonitride and a bonding phase containing nickel, niobium, and chromium, a nickel lattice constant of not less than 3.54 ⁇ results in a gold color tone with little color variation.
  • Sample 1-6 is not part of the invention.
  • each of the samples was measured using XRD (D8 ADVANCE, manufactured by Bruker AXS GmbH), and the presence of a titanium carbonitride crystal phase was verified. The lattice constant of titanium carbonitride was also verified. Additionally, each of the samples was measured using ICP, and the contents of nickel, niobium, and chromium were determined.
  • Molybdenum powder, tungsten powder, and cobalt powder were prepared, and samples were produced by reducing titanium carbide powder by 1 mass% in the starting raw material composition of Sample No. 4 of Example 1 and adding an equivalent amount of molybdenum powder, tungsten powder, or cobalt powder to each sample. Other than the starting raw material composition, the samples were prepared by the same method as Sample No. 4 of Example 1. For comparison, Sample No. 4 of Example 1 was also prepared.
  • the relative density of the obtained samples was then verified. Note that for relative density, the apparent density of a titanium nitride sintered compact was determined according to JIS R 1634-1998, and relative density was determined by dividing this apparent density by the theoretical density of the titanium nitride sintered compact. As a result, it was found that the each of the samples, to which molybdenum powder, tungsten powder, or cobalt powder was added, had a higher relative density than Sample No. 4, and that it is possible to reduce the firing temperature by including at least one type selected from the group consisting of molybdenum, tungsten, and cobalt in the titanium nitride sintered compact. It was also found that a decrease in shape processability due to abnormal grain growth of titanium carbonitride can be suppressed by reducing the firing temperature.
  • Samples were produced with varying time to hold the temperature at 400 to 600°C when increasing the temperature of firing, and color variation was verified.
  • the production method was the same as that of Sample No. 4 of Example 1, except for the hold time.
  • the hold time at 400 to 600°C was 25 minutes when increasing the temperature of firing, and for another sample, it was 50 minutes.
  • Sample Nos. 12 to 16 were obtained by the same method as Sample No. 4 of Example 1 except that the hold time in degreasing during firing was varied. Note that Sample No. 14 is a sample produced under the same conditions as Sample No. 4.
  • each of the samples was ground, and the free carbon content was determined by measurement using a carbon analyzer (RC-612, manufactured by LECO Corporation). Note that the content was determined from a calibration curve created using a standard sample (calcium carbonate), and the validity of the calibration curve was confirmed by measuring silicon carbide powder of known free carbon content.
  • Test pieces conforming to JIS R 1601-2008 were produced under the same conditions as when producing each of the samples. Three-point bending strength was measured, and the pieces were ranked from the highest value.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Metallurgy (AREA)
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Claims (4)

  1. Ein Cermet-Zierelement, aufweisend ein Sinterkörper-Cermet,
    wobei das Sinterkörper-Cermet aufweist:
    eine Kristallphase, die Titancarbonitrid enthält, und
    eine Bindephase, die mindestens ein Metall enthält,
    wobei die Bindephase aufweist:
    Nickel als eine Hauptkomponente, mit einer Gitterkonstante von 3,54 Å oder mehr, bestimmt mittels eines Röntgendiffraktometers,
    Niob und
    Chrom,
    wobei die Titancarbonitrid-Kristallphase eine Gitterkonstante von 4,27 Å oder mehr und 4,30 Å oder weniger hat, bestimmt mittels eines Röntgendiffraktometers,
    wobei ein Gehalt an Sauerstoff weniger als 1,0 Masse-% pro 100 Masse-% aller bildenden Komponenten ist,
    wobei ein Gehalt an freiem Kohlenstoff nicht kleiner als 1,5 Masse-% und nicht größer als 2,5 Masse-% pro 100 Masse-% aller Komponenten im Cermet ist,
    wobei Nickel in einer Menge von 7,0 bis 11,0 Masse-% vorhanden ist, Niob in einer Menge von 1,5 bis 6,0 Masse-% vorhanden ist, Chrom in einer Menge von 1,0 bis 5,0 Masse-% vorhanden ist, und der Rest Titancarbonitrid ist, pro 100 Masse-% aller Komponenten, die das Cermet bilden,
    wobei das Cermet mindestens eines von Molybdän, Wolfram und Cobalt enthält, und
    wobei Molybdän in einer Menge von 0,5 bis 2,0 Masse-% vorhanden ist, Wolfram in einer Menge von 0,05 bis 0,4 Masse-% vorhanden ist, und Cobalt in einer Menge von 0,02 Masse-% bis 0,2 Masse-% vorhanden ist, pro 100 Masse-% aller Komponenten, die das Cermet bilden.
  2. Eine Uhr, aufweisend das Cermet-Zierelement gemäß Anspruch 1.
  3. Ein mobiles Endgerät, aufweisend das Cermet-Zierelement gemäß Anspruch 1.
  4. Ein Zubehörteil, aufweisend das Cermet-Zierelement gemäß Anspruch 1.
EP16755638.0A 2015-02-26 2016-02-25 Zierelement aus cermet und uhr, tragbares endgerät und daraus erhaltenes zubehör Active EP3249066B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015036810 2015-02-26
PCT/JP2016/055670 WO2016136894A1 (ja) 2015-02-26 2016-02-25 サーメット製装飾部材ならびにこれを用いてなる時計、携帯端末機および装身具

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EP3249066A1 EP3249066A1 (de) 2017-11-29
EP3249066A4 EP3249066A4 (de) 2018-02-14
EP3249066B1 true EP3249066B1 (de) 2019-05-22

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Citations (1)

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JP2011047033A (ja) * 2009-07-27 2011-03-10 Kyocera Corp 装飾部品用セラミックスおよびこれを用いた装飾部品

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2183549A1 (en) * 1972-05-10 1973-12-21 Ugine Carbone Sintered metalcarbonitride material - for watch cases
JPS597341B2 (ja) * 1978-09-25 1984-02-17 三菱マテリアル株式会社 耐食性のすぐれた硬質焼結合金
JPH08199283A (ja) * 1994-07-29 1996-08-06 Hokkaido Sumiden Seimitsu Kk 炭窒化チタン基合金
JP4596692B2 (ja) * 2001-06-28 2010-12-08 京セラ株式会社 焼結合金及びその製造方法
EP2298948B1 (de) * 2008-05-28 2019-05-01 Kyocera Corporation Keramik für ein dekoratives element und dekoratives element dasselbe umfassend
JP5404643B2 (ja) * 2008-10-29 2014-02-05 京セラ株式会社 装飾部品用セラミックスおよび装飾部品
JP2011130894A (ja) * 2009-12-24 2011-07-07 Kyocera Corp 装飾部品用駒成形体およびこれを焼成してなる装飾部品用駒
WO2012121023A1 (ja) * 2011-03-07 2012-09-13 住友電工ハードメタル株式会社 装飾部品用材料
EP3040433B1 (de) * 2013-08-30 2018-05-23 Kyocera Corporation Dekorative komponente und uhr damit, tragbares endgerät und persönliches ornament

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011047033A (ja) * 2009-07-27 2011-03-10 Kyocera Corp 装飾部品用セラミックスおよびこれを用いた装飾部品

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